CN111065967A - Positive resist composition, method for forming resist film, and method for producing laminate - Google Patents

Positive resist composition, method for forming resist film, and method for producing laminate Download PDF

Info

Publication number
CN111065967A
CN111065967A CN201880058649.5A CN201880058649A CN111065967A CN 111065967 A CN111065967 A CN 111065967A CN 201880058649 A CN201880058649 A CN 201880058649A CN 111065967 A CN111065967 A CN 111065967A
Authority
CN
China
Prior art keywords
molecular weight
test examples
retention
average molecular
weight average
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201880058649.5A
Other languages
Chinese (zh)
Other versions
CN111065967B (en
Inventor
星野学
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zeon Corp
Original Assignee
Zeon Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zeon Corp filed Critical Zeon Corp
Publication of CN111065967A publication Critical patent/CN111065967A/en
Application granted granted Critical
Publication of CN111065967B publication Critical patent/CN111065967B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/085—Photosensitive compositions characterised by adhesion-promoting non-macromolecular additives
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/325—Non-aqueous compositions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

The invention provides a positive resist composition and the like, which can be heated at a heating temperature and a heating time in a pre-baking process (heating temperature in a range of a lower temperature side) in a wider range) The method improves the adhesion between the resist film formed through the pre-baking step and the workpiece, and reduces the change of the polymer molecular weight in the resist film before and after the pre-baking step. The positive resist composition of the present invention comprises a polymer having a monomer unit (A) represented by the following general formula (I) and a monomer unit (B) represented by the following general formula (II), and a solvent which is at least 1 selected from the group consisting of isoamyl acetate, n-butyl formate, isobutyl formate, n-pentyl formate and isoamyl formate.
Figure DDA0002405838410000011

Description

Positive resist composition, method for forming resist film, and method for producing laminate
Technical Field
The present invention relates to a positive resist composition, a resist film forming method, and a method for producing a laminate, and particularly relates to a positive resist composition, a resist film forming method using the positive resist composition, and a laminate producing method using the resist film forming method.
Background
Conventionally, in the field of semiconductor manufacturing and the like, a polymer having a main chain cut-off type, in which the main chain is cut off by irradiation with ionizing radiation such as an electron beam or light having a short wavelength such as ultraviolet light (hereinafter, the ionizing radiation and the light having a short wavelength are sometimes referred to as "ionizing radiation and the like"), has been used as a positive resist having a main chain cut-off type, and thus has increased solubility in a developer.
Further, for example, patent document 1 discloses a positive resist containing a α -methylstyrene α -chloroacrylic acid methyl ester copolymer containing α -methylstyrene units and α -chloroacrylic acid methyl ester units as a highly sensitive main chain cleavage type positive resist.
Documents of the prior art
Patent document
Patent document 1: japanese examined patent publication (Kokoku) No. 8-3636.
Disclosure of Invention
Problems to be solved by the invention
In a process for forming a resist film using a resist composition, when the resist composition is applied to a workpiece and then the resist film is formed through a pre-baking step of heating the applied resist composition, adhesion between the resist film and the workpiece may be insufficient or the molecular weight of a polymer in the resist film may be reduced. Here, when the adhesion between the resist film and the workpiece is insufficient, the resist film may be peeled off, and when the molecular weight of the polymer is lowered, a pattern having a desired shape cannot be formed. Therefore, formation of a resist film requires sufficient adhesion between the resist film formed through the prebaking step and the workpiece, and further, it is required to suppress a change in the molecular weight of the polymer in the resist film before and after the prebaking step.
However, in the resist film forming method using a positive resist containing α -methylstyrene α -methyl chloroacrylate copolymer described in patent document 1, there is a problem that the adhesion between the resist film formed through the pre-baking step and the workpiece is insufficient, and the change in the molecular weight of the polymer in the resist film before and after the pre-baking step cannot be sufficiently suppressed.
In order to solve the above problems, studies have been made on improving the adhesion between the resist film formed through the prebaking step and the workpiece and reducing the change in the molecular weight of the polymer in the resist film before and after the prebaking step by using n-hexyl acetate or the like as a solvent, but when these solvents are used, although the adhesion between the resist film formed through the prebaking step and the workpiece can be improved and the change in the molecular weight of the polymer in the resist film before and after the prebaking step can be reduced, the ranges of the heating temperature and the heating time in the prebaking step in which the adhesion can be improved and the change in the molecular weight can be reduced are narrow.
Accordingly, an object of the present invention is to provide a positive resist composition which can improve the adhesion between a resist film formed through a pre-baking step and a workpiece in a wider range of heating temperature and heating time (heating temperature in a range on the lower temperature side) in the pre-baking step, and can reduce the change in the molecular weight of a polymer in the resist film before and after the pre-baking step.
Another object of the present invention is to provide a method for forming a resist film, which can improve adhesion between a resist film formed through a pre-baking step and a workpiece and can reduce a change in the molecular weight of a polymer in the resist film before and after the pre-baking step.
Another object of the present invention is to provide a method for producing a laminate in which a resist film formed through a pre-baking step has high adhesion to a light-shielding layer and a decrease in the molecular weight of a polymer in the resist film is suppressed.
Means for solving the problems
The present inventors have conducted intensive studies in order to achieve the above object. Then, the present inventors have found that a main chain cleavage type positive resist composition containing a predetermined polymer having a predetermined monomer unit and a predetermined solvent can improve the adhesion between a resist film formed through a pre-baking step and a workpiece and reduce the change in the molecular weight of the polymer in the resist film before and after the pre-baking step, at a heating temperature and a heating time (heating temperature in a range on the lower temperature side) in a wider range in the pre-baking step, and have completed the present invention.
That is, the present invention is directed to advantageously solving the above problems, and a positive resist composition of the present invention is characterized by comprising a polymer and a solvent, the polymer having a monomer unit (a) represented by the following general formula (I) and a monomer unit (B) represented by the following general formula (II),
[ chemical formula 1]
Figure BDA0002405838390000031
(in the formula (I), R1Is a chlorine atom, fluorine atom or fluorine atom substituted alkyl group, R2Is unsubstituted alkyl or alkyl substituted by fluorine atoms, R3And R4The hydrogen atom, fluorine atom, unsubstituted alkyl group or fluorine atom-substituted alkyl group may be the same or different from each other. )
[ chemical formula 2]
Figure BDA0002405838390000032
(in the formula (II), R5、R6、R8And R9Is a hydrogen atom, a fluorine atom, an unsubstituted alkyl group or a fluorine atom-substituted alkyl group, and R may be the same or different from each other7Is a hydrogen atom, an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom, p and q are integers of 0 to 5 inclusive, and p + q is 5. )
At least one of the monomer unit (A) and the monomer unit (B) has one or more fluorine atoms,
the solvent is at least 1 selected from isoamyl acetate, n-butyl formate, isobutyl formate, n-pentyl formate and isoamyl formate.
The main chain cleavage type positive resist composition containing a predetermined polymer having a predetermined monomer unit and a predetermined solvent can improve the adhesion between a resist film formed through a pre-baking step and a work and reduce the change in the molecular weight of the polymer in the resist film before and after the pre-baking step, at a heating temperature and a heating time in the pre-baking step (heating temperature in a range on the lower temperature side) in a wider range.
In the present invention, when p in formula (II) is 2 or more, a plurality of R' s6May be the same or different from each other, and when q in the formula (II) is 2 or more, a plurality of R' s7May be the same or different from each other.
In the positive resist composition of the present invention, R is preferably the above-mentioned1Is a chlorine atom. If R of the monomer unit (A)1The chlorine atom improves the main chain cleavage property of the polymer when the polymer is irradiated with ionizing radiation or the like. Therefore, a good positive resist film can be obtained. Further, R of the monomer unit (A)1The polymer which is a chlorine atom is easily prepared.
In the positive resist composition of the present invention, R is preferably the above-mentioned2Is an alkyl group substituted with a fluorine atom, the above-mentioned R3And R4Is a hydrogen atom or an unsubstituted alkyl group. If R of the monomer unit (A)2Is fluorine atom substituted alkyl, R3And R4Is a hydrogen atom or notThe substituted alkyl group can improve the cleavage of the main chain of the polymer when the polymer is irradiated with ionizing radiation or the like. Therefore, a good positive resist film can be obtained. In addition, R3And R4May be the same or different from each other.
Further, in the positive resist composition of the present invention, it is preferable that p is an integer of 1 to 5, and R is5And R7～R9The above-mentioned monomer unit (A) is a hydrogen atom or an unsubstituted alkyl group and has one or more fluorine atoms. If p of the monomer unit (B) is an integer of 1 to 5, R5And R7～R9When the monomer unit (a) has one or more fluorine atoms as a hydrogen atom or an unsubstituted alkyl group, the polymer can be easily produced, and the main chain cleavage property of the polymer can be improved when the polymer is irradiated with ionizing radiation or the like, thereby obtaining a good positive resist film.
Further, in the positive resist composition of the present invention, it is preferable that the number of fluorine atoms in the monomer unit (B) is 0 or 1. If the number of fluorine atoms in the monomer unit (B) is 0 or 1, a good positive resist film can be obtained.
In the positive resist composition of the present invention, R is preferably the above-mentioned2Is a pentafluoroalkyl group. If R of the monomer unit (A)2The pentafluoroalkyl group can sufficiently improve sensitivity and can form a pattern with improved resolution.
In the positive resist composition of the present invention, R is preferably the above-mentioned2Is 2,2,3,3, 3-pentafluoropropyl. If R of the monomer unit (A)2With 2,2,3,3, 3-pentafluoropropyl group, sensitivity can be sufficiently improved, and a pattern with further improved definition can be formed.
Further, in the positive resist composition of the present invention, it is preferable that the monomer unit (B) is a structural unit derived from α -methylstyrene or a structural unit derived from 4-fluoro- α -methylstyrene, and if the monomer unit (B) is a structural unit derived from α -methylstyrene, the ease of preparing a polymer can be improved and a good positive resist film can be obtained, and if the monomer unit (B) is a structural unit derived from 4-fluoro- α -methylstyrene, a pattern in which collapse is suppressed can be formed.
The present invention is also directed to a resist film forming method for forming a resist film using any one of the positive resist compositions, including:
a coating step of coating the positive resist composition on a workpiece,
a prebaking step of heating the applied positive resist composition,
the heating in the pre-baking step is performed at a temperature T (c) and a time T (min) satisfying the following formula (1).
(-1/4)×T+32.5≤t≤(-1/4)×T+55···(1)
When a predetermined polymer having a predetermined monomer unit is used as a main chain cleavage type positive resist and a prebaking process is performed under predetermined conditions, the adhesion between a resist film formed through the prebaking process and a workpiece can be improved and the change in the molecular weight of the polymer in the resist film before and after the prebaking process can be sufficiently suppressed.
In the resist film forming method of the present invention, the time is preferably 1 minute to 30 minutes. If the above-mentioned time is 1 minute or more and 30 minutes or less in the heating in the prebaking step, the adhesion between the resist film formed through the prebaking step and the workpiece can be more reliably improved, and the change in the molecular weight of the polymer in the resist film before and after the prebaking step can be more reliably reduced.
The present invention is also directed to a method for producing a laminate, the method comprising a substrate, a light-shielding layer formed on the substrate, and a resist film formed on the light-shielding layer, wherein the resist film is formed by any of the above-described resist film forming methods. When a resist film is formed by any of the above-described resist film forming methods, a laminate can be obtained in which the adhesion between the resist film formed through the prebaking step and the light-shielding layer is high and the decrease in the molecular weight of the polymer in the resist film is suppressed.
Effects of the invention
According to the positive resist composition of the present invention, it is possible to improve the adhesion between the resist film formed through the prebaking process and the workpiece in a wider range of heating temperature and heating time in the prebaking process (heating temperature in a range on the lower temperature side), and to reduce the change in the molecular weight of the polymer in the resist film before and after the prebaking process.
Further, according to the resist film forming method of the present invention, the adhesion between the resist film formed through the pre-baking step and the workpiece can be improved, and the change in the molecular weight of the polymer in the resist film before and after the pre-baking step can be reduced.
Further, according to the method for producing a laminate of the present invention, adhesion between the resist film formed through the prebaking step and the light shielding layer can be improved, and a decrease in the molecular weight of the polymer in the resist film can be suppressed.
Drawings
Fig. 1 is a diagram showing a relationship between a temperature T (c) in a prebaking step and a time T (minutes) in a resist film forming method using a positive resist composition of the present invention.
In fig. 2A, the upper graph shows the relationship between the temperature T (° c) in the prebaking step and the time T (minutes) in a resist film forming method using a positive resist composition containing a polymer (F5) and isoamyl acetate; the following figure is a graph showing the relationship between the temperature T (c) in the prebaking step and the time T (min) in a comparative resist film formation method using a positive resist composition containing polymer (F5) and n-hexyl acetate.
In fig. 2B, the upper diagram is a diagram showing the relationship between the temperature T (° c) in the prebaking step and the time T (minutes) in a resist film forming method using a positive resist composition containing a polymer (F5) and n-butyl formate; the following figure is a graph showing the relationship between the temperature T (c) in the prebaking step and the time T (min) in a comparative resist film formation method using a positive resist composition containing polymer (F5) and n-hexyl acetate.
FIG. 2C is a graph showing the relationship between the temperature T (. degree. C.) in the prebaking step and the time T (minute) in a resist film forming method using a positive resist composition containing a polymer (F5) and isobutyl formate; the following figure is a graph showing the relationship between the temperature T (c) in the prebaking step and the time T (min) in a comparative resist film formation method using a positive resist composition containing polymer (F5) and n-hexyl acetate.
In FIG. 2D, the upper graph shows the relationship between the temperature T (. degree. C.) in the prebaking step and the time T (minutes) in the resist film forming method using the positive resist composition containing the polymer (F5) and n-amyl formate; the following figure is a graph showing the relationship between the temperature T (c) in the prebaking step and the time T (min) in a comparative resist film formation method using a positive resist composition containing polymer (F5) and n-hexyl acetate.
FIG. 2E, the upper panel, is a graph showing the relationship between the temperature T (. degree. C.) in the prebaking step and the time T (minute) in a resist film forming method using a positive resist composition containing a polymer (F5) and isoamyl formate; the following figure is a graph showing the relationship between the temperature T (c) in the prebaking step and the time T (min) in a comparative resist film formation method using a positive resist composition containing polymer (F5) and n-hexyl acetate.
In fig. 3A, the upper graph shows the relationship between the temperature T (° c) in the prebaking step and the time T (minutes) in a resist film forming method using a positive resist composition containing a polymer (F6) and isoamyl acetate; the following figure is a graph showing the relationship between the temperature T (c) in the prebaking step and the time T (min) in a comparative resist film formation method using a positive resist composition containing polymer (F6) and n-hexyl acetate.
In fig. 3B, the upper graph shows the relationship between the temperature T (° c) in the prebaking step and the time T (minutes) in the resist film forming method using a positive resist composition containing the polymer (F6) and n-butyl formate; the following figure is a graph showing the relationship between the temperature T (c) in the prebaking step and the time T (min) in a comparative resist film formation method using a positive resist composition containing polymer (F6) and n-hexyl acetate.
FIG. 3C is a graph showing the relationship between the temperature T (. degree. C.) in the prebaking step and the time T (minute) in a resist film forming method using a positive resist composition containing a polymer (F6) and isobutyl formate; the following figure is a graph showing the relationship between the temperature T (c) in the prebaking step and the time T (min) in a comparative resist film formation method using a positive resist composition containing polymer (F6) and n-hexyl acetate.
In FIG. 3D, the upper graph shows the relationship between the temperature T (. degree. C.) in the prebaking step and the time T (minutes) in the resist film forming method using the positive resist composition containing the polymer (F6) and n-amyl formate; the following figure is a graph showing the relationship between the temperature T (c) in the prebaking step and the time T (min) in a comparative resist film formation method using a positive resist composition containing polymer (F6) and n-hexyl acetate.
In fig. 3E, the upper diagram is a diagram showing the relationship between the temperature T (° c) in the prebaking step and the time T (minutes) in a resist film forming method using a positive resist composition containing a polymer (F6) and isoamyl formate; the following figure is a graph showing the relationship between the temperature T (c) in the prebaking step and the time T (min) in a comparative resist film formation method using a positive resist composition containing polymer (F6) and n-hexyl acetate.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail.
Here, the resist composition of the present invention can be used in the resist film formation method of the present invention. The resist film forming method of the present invention can form, for example, the following resist films: it is used in the process of manufacturing a printed board such as a build-up board, etc., in forming a resist pattern. The method for producing a laminate of the present invention can produce, for example, the following laminates: it is used in the process of manufacturing a printed board such as a build-up board, etc., in forming a resist pattern.
The polymer in the resist composition of the present invention can be suitably used as a main chain-cut positive resist in which the main chain of the polymer is cut by irradiation with an electron beam, ionizing radiation such as EUV (extreme ultraviolet) laser, or short-wavelength light such as ultraviolet light to reduce the molecular weight.
(Positive resist composition)
The positive resist composition of the present invention comprises a polymer and a solvent, and further optionally contains known additives which can be compounded in the resist composition. Further, since the positive resist composition of the present invention contains a polymer described later as a positive resist, collapse of a resist pattern can be sufficiently suppressed when the composition is used for forming a resist pattern. Further, if the pre-baking is performed under the conditions described later, the adhesion can be improved and the decrease in the molecular weight of the polymer can be suppressed.
The solid content concentration of the positive resist composition is preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 3% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 5% by mass or less.
< polymers >
The polymer has a monomer unit (A) represented by the following general formula (I) and a monomer unit (B) represented by the following general formula (II),
[ chemical formula 3]
Figure BDA0002405838390000091
(in the formula (I), R1Is a chlorine atom, fluorine atom or fluorine atom substituted alkyl group, R2Is unsubstituted alkyl or alkyl substituted by fluorine atoms, R3And R4Is a hydrogen atom, a fluorine atom, an unsubstituted alkyl group or a fluorine atom-substituted alkyl group, R3And R4May be the same or different from each other)
[ chemical formula 4]
Figure BDA0002405838390000092
(in the formula (II), R5、R6、R8And R9Is a hydrogen atom, a fluorine atom, an unsubstituted alkyl group or a fluorine atom-substituted alkyl group, and R may be the same or different from each other7Is a hydrogen atom, an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom, p and q are integers of 0 to 5 inclusive, and p + q is 5).
In the above polymer, at least one of the monomer unit (a) and the monomer unit (B) has one or more fluorine atoms. That is, the polymer may be such that the monomer unit (a) has one or more fluorine atoms and the monomer unit (B) does not have a fluorine atom, the monomer unit (B) has one or more fluorine atoms and the monomer unit (a) does not have a fluorine atom, or the monomer unit (a) and the monomer unit (B) each have one or more fluorine atoms.
The polymer may contain optional monomer units other than the monomer unit (a) and the monomer unit (B), but the proportion of the monomer unit (a) and the monomer unit (B) in the total monomer units constituting the polymer is preferably 90 mol% or more in total, more preferably substantially 100 mol%, and still more preferably 100 mol% (that is, the polymer contains only the monomer unit (a) and the monomer unit (B)).
Since the polymer contains the predetermined monomer unit (a) and the predetermined monomer unit (B), when ionizing radiation or the like (for example, electron beam, KrF laser, ArF laser, EUV (extreme ultraviolet) laser, or the like) is irradiated, the main chain of the polymer can be cut to reduce the molecular weight. Further, since at least one of the monomer unit (a) and the monomer unit (B) in the polymer has one or more fluorine atoms, when used as a resist, the polymer has high heat resistance during prebaking, is suppressed from decomposition, can improve adhesion to a workpiece, and can sufficiently suppress collapse of a resist pattern.
Further, it is not clear why collapse of the resist pattern can be suppressed by making at least one of the monomer unit (a) and the monomer unit (B) have a fluorine atom, and it is presumed that since the liquid-repellency (liquid-repellant) of the polymer is improved, mutual pulling between the patterns can be suppressed when the developer and the rinse are removed during the formation of the resist pattern.
< monomer Unit (A) >
Here, the monomer unit (A) is a structural unit derived from a monomer (a) represented by the following general formula (III),
[ chemical formula 5]
Figure BDA0002405838390000101
(in the formula (III), R1～R4The same as formula (I). )
The proportion of the monomer unit (a) in the total monomer units constituting the polymer is not particularly limited, and may be, for example, 30 mol% or more and 70 mol% or less, and preferably 40 mol% or more and 60 mol% or less.
Here, R which may constitute the formula (I) and the formula (III)1～R4The fluorine atom-substituted alkyl group of (1) is not particularly limited, and examples thereof include groups having a structure in which a part or all of hydrogen atoms in the alkyl group are substituted with fluorine atoms.
Further, R as R in the formula (I) and the formula (III) may be constituted2～R4The unsubstituted alkyl group of (2) is not particularly limited, and examples thereof include unsubstituted alkyl groups having 1 to 10 carbon atoms. As can constitute R2～R4The unsubstituted alkyl group of (1) is particularly preferably a methyl group or an ethyl group.
Further, R in the formulae (I) and (III) is R in the formulae (I) and (III) from the viewpoint of improving the main chain cleavage property of the polymer when it is irradiated with ionizing radiation or the like1The alkyl group having 1 to 5 carbon atoms substituted with a chlorine atom, a fluorine atom or a fluorine atom is preferable, the alkyl group is more preferably a chlorine atom, a fluorine atom or a perfluoromethyl group, the alkyl group is more preferably a chlorine atom or a fluorine atom, and the alkyl group is particularly preferably a chlorine atom. In addition, R in the formula (III)1The monomer (a) having a chlorine atom is excellent in polymerizability and has R in the formula (I)1The polymer of the monomer unit (a) which is a chlorine atom is also excellent in terms of ease of preparation.
Further, from the viewpoint of improving the main chain cleavage property of the polymer when it is irradiated with ionizing radiation or the like, the formula (I)) And R in the formula (III)2The alkyl group is preferably a fluorine atom-substituted alkyl group, and more preferably a fluorine atom-substituted alkyl group having 1 to 10 carbon atoms.
Examples of the alkyl group having 1 to 10 carbon atoms substituted with a fluorine atom include a pentafluoroalkyl group such as a 2,2, 2-trifluoroethyl group, a 2,2,3,3, 3-pentafluoropropyl group (the following structural formula X having 5 carbon atoms and 3 carbon atoms), a 2- (perfluorobutyl) ethyl group, a 2- (perfluorohexyl) ethyl group, a 1H,1H, 3H-tetrafluoropropyl group, a 1H,1H, 5H-octafluoropentyl group, a 1H,1H, 7H-dodecafluoroheptyl group, a 1H-1- (trifluoromethyl) trifluoroethyl group, a 1H,1H, 3H-hexafluorobutyl group, a1, 2,2, 2-tetrafluoro-1- (trifluoromethyl) ethyl group and the like.
Among these, a pentafluoroalkyl group is preferable, and a 2,2,3,3, 3-pentafluoropropyl group (the following structural formula X having 5 fluorine atoms and 3 carbon atoms) is particularly preferable.
[ chemical formula 6]
Figure BDA0002405838390000111
Further, from the viewpoint of improving the main chain cleavage property of the polymer when it is irradiated with ionizing radiation or the like, R in the formulae (I) and (III)3And R4Each of these groups is preferably a hydrogen atom or an unsubstituted alkyl group, more preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms, and still more preferably a hydrogen atom.
The monomer (a) represented by the formula (I) which can form the monomer unit (A) represented by the formula (I) is not particularly limited, and examples thereof include α -chloroacrylic acid-2, 2, 2-trifluoroethyl ester, α -chloroacrylic acid-2, 2,3,3, 3-pentafluoropropyl ester, α -chloroacrylic acid-2- (perfluorobutyl) ethyl ester, α -chloroacrylic acid-2- (perfluorohexyl) ethyl ester, α -chloroacrylic acid-1H, 1H, 3H-tetrafluoropropyl ester, α -chloroacrylic acid-1H, 1H, 5H-octafluoropentyl ester, α -chloroacrylic acid-1H, 1H, 7H-dodecafluoroheptyl ester, 639-chloroacrylic acid-1H-1- (trifluoromethyl) trifluoroethyl ester, α -chloroacrylic acid-1H, 1H, 3H-hexafluorobutyl ester, α -chloroacrylic acid-1, 2, 6862, 2-tetrafluoro-1- (trifluoromethyl) trifluoroethyl ester, 366-chloroacrylic acid-1H, α -fluorohexyl ester, α -fluorohexyl acrylate, α -3-fluorohexyl acrylate, α -fluorohexyl-3-fluorohexyl-1H- α, α -fluorohexyl acrylate, α -3-fluorohexyl-3-fluorooctyl ester, α -fluorohexyl acrylate, α -fluorohexyl-3-fluorohexyl acrylate, α -fluorohexyl-3-fluorooctyl ester, α -3-fluorohexyl-fluorooctyl ester, α -fluorohexyl acrylate, α -fluorohexyl acrylate, α -fluorooctyl ester, α -3-fluorohexyl acrylate, α -fluorohexyl-3-fluorohexyl acrylate, α -3-fluorohexyl-3-fluorooctyl ester, α -fluorohexyl-fluorooctyl ester, α -fluorohexyl-3-fluorohexyl-3-.
In addition, from the viewpoint of further improving the main chain cleavage property of the polymer upon exposure to ionizing radiation or the like, the monomer unit (A) is preferably a structural unit derived from α -chloroacrylic acid fluoroalkyl ester, and particularly preferably α -chloroacrylic acid-2, 2,3,3, 3-pentafluoropropyl ester, that is, R in the formulae (I) and (III)1～R4Particular preference is given to R1Is a chlorine atom, R2Is fluorine atom substituted alkyl, R3And R4Is a hydrogen atom.
< monomer Unit (B) >
Further, the monomer unit (B) is a structural unit derived from a monomer (B) represented by the following general formula (IV),
[ chemical formula 7]
Figure BDA0002405838390000121
(in the formula (IV), R5～R9And p and q are the same as formula (II). ).
The proportion of the monomer unit (B) in the total monomer units constituting the polymer is not particularly limited, and may be, for example, 30 mol% or more and 70 mol% or less, and preferably 40 mol% or more and 60 mol% or less.
Here, R in the formula (II) and the formula (IV) may be constituted5～R9The fluorine atom-substituted alkyl group of (2) is not particularly limited, and examples thereof include groups having a structure in which a part or all of hydrogen atoms in the alkyl group are substituted with fluorine atoms.
In addition, asCan constitute R in formula (II) and formula (IV)5～R9The unsubstituted alkyl group of (2) is not particularly limited, and examples thereof include unsubstituted alkyl groups having 1 to 5 carbon atoms. Wherein R may be a group5～R9Preferably methyl or ethyl.
Further, R in the formula (II) and the formula (IV) is R in the formula (II) and the formula (IV) from the viewpoints of improving the easiness of producing the polymer and the main chain cleavage property of the polymer upon irradiation with ionizing radiation or the like5The alkyl group is preferably a hydrogen atom or an unsubstituted alkyl group, more preferably an unsubstituted alkyl group having 1 to 5 carbon atoms, and still more preferably a methyl group.
A plurality of R present in the formulae (II) and (IV)7The alkyl group may be a hydrogen atom or an unsubstituted alkyl group, or a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms, or a hydrogen atom. This can improve the ease of production of the polymer and the main chain cleavage property of the polymer when the polymer is irradiated with ionizing radiation or the like.
In the formulae (II) and (IV), p is 5, q is 0, and 5R6May be all hydrogen atoms or unsubstituted alkyl groups, 5R6The alkyl group may be a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms, and 5R' s6And may also be all hydrogen atoms. This can improve the ease of production of the polymer and the ability to cleave the main chain of the polymer when the polymer is irradiated with ionizing radiation or the like.
On the other hand, the plurality of R present in the formulae (II) and (IV) are from the viewpoint of further suppressing collapse of the resist pattern when the polymer is used for forming the resist pattern6And/or R7Preferably a fluorine atom-or fluorine atom-substituted alkyl group, more preferably a fluorine atom-or fluorine atom-substituted alkyl group having 1 to 5 carbon atoms, and particularly preferably R6And/or R7The number of fluorine atoms in (1).
Further, from the viewpoints of improving the ease of producing the polymer and the main chain cleavage property of the polymer upon irradiation with ionizing radiation or the like, R in the formulae (II) and (IV)8And R9Preferably independently of each other a hydrogen atom or unsubstitutedThe alkyl group of (3) is more preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms, and still more preferably a hydrogen atom.
The monomer (B) represented by the formula (IV) which can form the monomer unit (B) represented by the formula (II) is not particularly limited, and examples thereof include α -methylstyrene and derivatives thereof such as the following (B-1) to (B-11).
The number of fluorine atoms in the monomer unit (B) is preferably 0 or 1.
[ chemical formula 8]
Figure BDA0002405838390000141
In addition, from the viewpoint of improving the ease of producing a polymer and the main chain cleavage property of the polymer upon irradiation with ionizing radiation or the like, the polymer unit (B) preferably does not contain a fluorine atom (i.e., only the monomer unit (A) contains a fluorine atom), and more preferably is a structural unit derived from α -methylstyrene, i.e., R in the formulae (II) and (IV)5～R9And p and q are particularly preferably p-5, q-0, R5Is methyl, 5R6Are each a hydrogen atom, R8And R9Is a hydrogen atom.
On the other hand, from the viewpoint of further suppressing collapse of the resist pattern when the polymer is used for forming the resist pattern, the monomer unit (B) preferably contains a fluorine atom, more preferably contains 1 fluorine atom, particularly preferably a structural unit derived from fluorine- α -methylstyrene, and most preferably a structural unit derived from 4-fluorine- α -methylstyrene, that is, R in the formula (II) and the formula (IV)5～R9And p and q are most preferably p-5, q-0, R5Is methyl, 5R6Wherein only the para-position is fluorine, the remaining 4 are hydrogen atoms, R8And R9Is a hydrogen atom.
< Properties of Polymer >
Hereinafter, properties of the polymer used in the resist film forming method of the present invention, that is, "weight average molecular weight (Mw)", "number average molecular weight (Mn)" and "molecular weight distribution (Mw/Mn)" before heating in the prebaking step will be described.
In the present invention, "weight average molecular weight (Mw)" and "number average molecular weight (Mn)" can be measured by gel permeation chromatography. In the present invention, the "molecular weight distribution (Mw/Mn)" refers to the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
[ weight average molecular weight ]
The weight average molecular weight (Mw) of the polymer having the monomer units (a) and (B) may be, for example, 20000 or more and 150000 or less. Further, the weight average molecular weight (Mw) of the polymer is preferably less than 100000, more preferably less than 60000, and preferably 30000 or more. When the weight average molecular weight (Mw) of the polymer is not more than the upper limit (less than) described above, the solubility in a developer can be increased with a low irradiation dose when used as a positive resist, and thus the sensitivity when used as a positive resist can be suitably improved. Further, if the weight average molecular weight (Mw) of the polymer is not less than the above lower limit, the solubility of the resist film in the developer can be inhibited from being improved by an excessively low irradiation amount, and the γ value can be inhibited from being excessively low.
[ number average molecular weight ]
The number average molecular weight (Mn) of the polymer may be, for example, 10000 or more and 100000 or less. Further, the number average molecular weight (Mn) of the polymer is preferably less than 80000, more preferably less than 50000. If the number average molecular weight (Mn) of the polymer is not more than the above upper limit (less than), the sensitivity when a resist formed using a positive resist composition containing the polymer is used as a positive resist can be further improved.
[ molecular weight distribution ]
The molecular weight distribution (Mw/Mn) of the polymer may be, for example, 2.50 or less. Further, the molecular weight distribution (Mw/Mn) of the polymer is preferably 1.20 or more, more preferably 1.30 or more, particularly preferably 1.35 or more, preferably 2.40 or less, more preferably 1.75 or less, further preferably 1.60 or less, and further preferably 1.55 or less. When the molecular weight distribution (Mw/Mn) of the polymer is not less than the lower limit, the ease of producing the polymer can be improved. When the molecular weight distribution (Mw/Mn) of the polymer is not more than the above upper limit, the γ value in the case of using as a positive resist can be increased, and the resolution of the obtained resist pattern can be improved.
< preparation method of Polymer >)
The polymer having the monomer unit (a) and the monomer unit (B) can be produced, for example, by polymerizing a monomer composition containing the monomer (a) and the monomer (B) and then optionally purifying the resulting polymer.
The composition, molecular weight distribution, weight average molecular weight, and number average molecular weight of the polymer can be adjusted by changing the polymerization conditions and purification conditions. Specifically, for example, the composition of the polymer can be adjusted by changing the content ratio of each monomer in the monomer composition used for polymerization. Further, if the polymerization temperature is increased, the weight average molecular weight and the number average molecular weight can be reduced. Further, if the polymerization time is shortened, the weight average molecular weight and the number average molecular weight can be reduced.
[ polymerization of monomer composition ]
Here, as the monomer composition for preparing the polymer of the present invention, a mixture of monomer components comprising the monomer (a) and the monomer (b), an optional solvent, a polymerization initiator, and an optional additive may be used. Further, the polymerization of the monomer composition can be carried out using a known method. Among them, cyclopentanone or the like is preferably used as the solvent, and a radical polymerization initiator such as azobisisobutyronitrile or the like is preferably used as the polymerization initiator.
The polymerization product obtained by polymerizing the monomer composition is not particularly limited, and can be recovered by adding a good solvent such as tetrahydrofuran to a solution containing the polymer, and then dropwise adding the solution to which the good solvent has been added to a poor solvent such as methanol to coagulate the polymerization product.
< purification of polymerization product >)
The purification method used for purifying the obtained polymer product is not particularly limited, and known purification methods such as reprecipitation and column chromatography may be mentioned. As the purification method, a reprecipitation method is particularly preferably used.
Further, the purification of the polymerization product may be repeated a plurality of times.
Further, the purification of the polymerization product by reprecipitation is preferably carried out by, for example: the obtained polymer is dissolved in a good solvent such as tetrahydrofuran, and the resulting solution is added dropwise to a mixed solvent of the good solvent such as tetrahydrofuran and a poor solvent such as methanol to partially precipitate the polymer. In this way, if the solution of the polymerization product is dropped into the mixed solvent of the good solvent and the poor solvent to purify the polymerization product, the molecular weight distribution, the weight average molecular weight, and the number average molecular weight of the obtained polymer can be easily adjusted by changing the kind and the mixing ratio of the good solvent and the poor solvent. Specifically, for example, the higher the proportion of the good solvent in the mixed solvent, the higher the molecular weight of the polymer precipitated in the mixed solvent can be.
In the case of purifying the polymer product by the reprecipitation method, the polymer product precipitated in a mixed solvent of a good solvent and a poor solvent may be used as the polymer, or a polymer product not precipitated from the mixed solvent (that is, a polymer product dissolved in the mixed solvent) may be used. The polymerization product that has not precipitated from the mixed solvent can be recovered from the mixed solvent by a known method such as concentration and drying.
< solvent >
As the solvent, at least 1 selected from the group consisting of isoamyl acetate (boiling point: 142 ℃ C., surface tension: 24.6mN/m), n-butyl formate (boiling point: 107 ℃ C., surface tension: 25mN/m), isobutyl formate (boiling point: 98.4 ℃ C., surface tension: 23.7mN/m), n-pentyl formate (boiling point: 132 ℃ C., surface tension: 26mN/m) and isoamyl formate (boiling point: 124 ℃ C., surface tension: 24.6mN/m) can be used.
By using the solvent, even when a polymer having the monomer unit (a) and the monomer unit (B) is used as a positive resist, the adhesion between the resist film formed through the prebaking step and the workpiece can be improved in a wider range of heating temperature and heating time (heating temperature in a range on the lower temperature side) in the prebaking step, and the change in the molecular weight of the polymer in the resist film before and after the prebaking step can be reduced.
Among them, from the viewpoint of improving the film thickness accuracy of the formed resist film, a monomer or a mixture of a amyl solvent (isoamyl acetate, n-amyl formate, and isoamyl formate) is preferable as the solvent, a monomer or a mixture of an isoamyl solvent (isoamyl acetate, isoamyl formate) is more preferable from the viewpoint of no malodor, and isoamyl acetate is particularly preferable from the viewpoint of easy availability.
As described above, the solvent may be a mixture, but from the viewpoint of easiness of recovery and reuse of the solvent, a single solvent formed of a single substance is preferable.
< boiling point of solvent >)
The boiling point of the solvent is not particularly limited and may be appropriately selected according to the purpose, and is preferably 110 ℃ or higher and 160 ℃ or lower, and more preferably 120 ℃ or higher and 150 ℃ or lower, from the viewpoint of improving the film thickness accuracy of the formed resist film.
The boiling point at 1 atm is based on a general literature value described in a solvent handbook (published by KODANSHA ltd).
< surface tension of solvent >)
The surface tension of the solvent is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 32mN/m or less from the viewpoint of improving the wettability of the resist composition to the substrate and the film thickness accuracy of the formed resist film, and more preferably 29mN/m or less from the viewpoint of obtaining a positive resist solution having an appropriate viscosity and improving the coatability of the positive resist solution.
The surface tension is a value measured by the pendant Drop method (pendant Drop method) at 23 ℃ using Drop Master700(Kyowa Interface Science, Inc.).
(resist film formation method)
The resist film forming method of the present invention is a resist film forming method for forming a resist film using the positive resist composition of the present invention, and includes a coating step of coating the positive resist composition on a workpiece, and a prebaking step of heating the coated positive resist composition at a temperature T (deg.c) and a time T (minutes) satisfying the following formula (1) (in a region between a straight line P and a straight line U in the drawing of fig. 1).
(-1/4)×T+32.5≤t≤(-1/4)×T+55···(1)
Wherein t >0
< coating Process >
In the coating step, the positive resist composition is coated on a workpiece such as a substrate to be processed by a resist pattern. The coating method is not particularly limited, and may be carried out by a known coating method.
The workpiece to which the positive resist composition is applied may be a substrate, or may be a "Mask Blanks (masks)" in which a light shielding layer is formed on the substrate.
< Pre-baking step >
In the prebaking step, the applied positive resist composition is heated (prebaked) to form a resist film.
Here, heating (prebaking) is performed at a temperature T (° c) and for a time T (minutes) satisfying the following formula (1). Here, the temperature T (° c) and the time T (minutes) satisfying the following formula (1) mean "in the graph of fig. 1, the temperature T (° c) and the time T (minutes) exist between the straight line P and the straight line U". This improves the adhesion between the resist film and the workpiece, and reduces the change in the molecular weight of the polymer in the resist film before and after the pre-baking step.
(-1/4)×T+32.5≤t≤(-1/4)×T+55···(1)
Further, the temperature T (. degree. C.) and the time T (minute) preferably satisfy the following formula (2), more preferably satisfy the following formula (3), particularly preferably satisfy the following formula (4), and preferably satisfy the following formula (5), more preferably satisfy the following formula (5-2), still more preferably satisfy the following formula (6), particularly preferably satisfy the following formula (7).
(-1/4)T+35≤t···(2)
(-1/4)T+37.5≤t···(3)
(-1/4)T+40≤t···(4)
t≤(-7/30)T+142/3···(5)
t≤(-3/10)T+58···(5-2)
t<(-7/10)T+115···(6)
t<(-8/15)T+262/3···(7)
When the pre-baking (heating) is performed at a temperature T (deg.c) and a time T (min) that satisfy the above-described formulae (1) and (6) (in the graph of fig. 1, the temperature T (deg.c) and the time T (min) exist between the line P and the line C), by heating at a lower temperature side, it is possible to maintain the adhesion between the resist film and the object to be processed, and to reliably reduce the change in the polymer molecular weight in the resist film before and after the pre-baking step.
When the pre-baking (heating) is performed at a temperature T (c) and a time T (min) that satisfy the above formula (1) and the above formula (7) (in the graph of fig. 1, the temperature T (c) and the time T (min) exist between the line P and the line a), by performing the heating on the further low temperature side, the adhesion between the resist film and the work can be maintained, and the change in the polymer molecular weight in the resist film before and after the pre-baking step can be more reliably reduced.
The straight lines A, C, P to U in FIGS. 1 to 3E are represented by the following formulae.
A straight line A: t (-8/15) T +262/3
A straight line C: t (-7/10) T +115
A straight line P: t (-1/4) T +32.5
A straight line Q: t (-1/4) T +35
A straight line R: t (-1/4) T +37.5
A straight line S: t (-1/4) T +40
A straight line T: t (-3/10) T +58
Straight line T2: t (-7/30) T +142/3
A straight line U: t (-1/4) T +55
Further, the temperature T (deg.c) is preferably 110 deg.c or more, more preferably 115 deg.c or more, and even more preferably 120 deg.c or more from the viewpoint of adhesion between the resist film formed through the pre-baking step and the object to be processed, and is preferably 180 deg.c or less, more preferably 170 deg.c or less from the viewpoint of reducing the change in the molecular weight of the polymer in the resist film before and after the pre-baking step. The time t (min) is preferably 1 min or more, more preferably 3 min or more, and still more preferably 5 min or more from the viewpoint of adhesion between the resist film formed through the prebaking step and the workpiece, and is preferably 30 min or less, more preferably 10 min or less from the viewpoint of reducing the change in the molecular weight of the polymer in the resist film before and after the prebaking step.
Hereinafter, the properties of the polymer after heating in the prebaking step, that is, "weight average molecular weight (Mw)", "number average molecular weight (Mn)" and "molecular weight distribution (Mw/Mn)" of the polymer will be described.
[ weight average molecular weight ]
The weight average molecular weight (Mw) of the polymer in the resist film formed by the resist film forming method using the positive resist composition of the present invention (i.e., the resist film formed through the prebaking step) may be, for example, 45900 or more and 59000 or less. Further, the weight average molecular weight (Mw) of the polymer in the resist film formed through the prebaking step is preferably 52000 or less, and preferably 46500 or more. If the weight average molecular weight (Mw) of the polymer in the resist film formed through the prebaking step is not more than the above upper limit value (less than), the sensitivity of the resist film can be improved. In addition, if the weight average molecular weight (Mw) of the polymer in the resist film formed through the prebaking step is not less than the above-described lower limit, it can be prevented from dissolving in the developer.
[ number average molecular weight ]
The number average molecular weight (Mn) of the polymer in the resist film formed by the resist film forming method using the positive resist composition of the present invention (i.e., the resist film formed through the prebaking step) may be, for example, 34400 or more and 43500 or less. Further, the number average molecular weight (Mn) of the polymer in the resist film formed through the prebaking step is preferably 41600 or less, and preferably 36500 or more. If the number average molecular weight (Mn) of the polymer in the resist film formed through the prebaking process is not more than the above upper limit value (less than), the sensitivity of the resist film can be improved. In addition, if the number average molecular weight (Mn) of the polymer in the resist film formed through the prebaking step is not less than the above-described lower limit, it can be prevented from dissolving in the developer.
[ molecular weight distribution ]
The molecular weight distribution (Mw/Mn) of the polymer in the resist film formed by the resist film forming method using the positive resist composition of the present invention (i.e., the resist film formed through the prebaking step) may be, for example, 1.50 or less. Further, the molecular weight distribution (Mw/Mn) of the polymer in the resist film formed through the prebaking step is preferably 1.28 or more, more preferably 1.30 or more, preferably 1.45 or less, more preferably 1.40 or less. If the molecular weight distribution (Mw/Mn) of the polymer in the resist film formed through the prebaking step is not less than the above lower limit, the prebaking time can be shortened. When the molecular weight distribution (Mw/Mn) of the polymer is not more than the above upper limit, a clear pattern can be obtained at the time of forming a pattern.
The retention of the weight average molecular weight of the polymer heated in the prebaking step (weight average molecular weight of the polymer after heating in the prebaking step/weight average molecular weight of the polymer before heating in the prebaking step) is preferably 95.7% or more, more preferably 96.0% or more, particularly preferably 97.0% or more, and most preferably 99.0% or more.
< method for Forming resist Pattern >
The resist pattern forming method preferably includes (1) a step of forming a resist film by the above-described resist film forming method, (2) a step of exposing the resist film, and (3) a step of developing the exposed resist film.
< Exposure Process >
In the step (2), the resist film is irradiated with ionizing radiation or light to draw a desired pattern. For irradiation with ionizing radiation or light, a known drawing device such as an electron beam drawing device or a laser drawing device can be used.
< developing Process >)
In the step (3), the patterned resist film is brought into contact with a developer to develop the resist film, thereby forming a resist pattern on the workpiece. Here, the method of bringing the resist film into contact with the developer is not particularly limited, and known methods such as dipping the resist film in the developer and applying the developer to the resist film can be used. Further, the developed resist film is optionally rinsed with a rinsing liquid.
Particularly, as the developing solution and the rinse solution, for example, those containing CF can be used3CFHCFHCF2CF3、CF3CF2CHCl2、CClF2CF2CHClF、CF3CF2CF2CF2OCH3And C8F18Fluorine-based solvents such as fluorocarbon compounds of (1); alcohols such as methanol, ethanol, 1-propanol, and 2-propanol (isopropanol); acetates having an alkyl group such as amyl acetate and hexyl acetate; a mixture of a fluorine-based solvent and an alcohol; a mixture of a fluorine-based solvent and an acetate having an alkyl group; a mixture of an alcohol and an acetate having an alkyl group; a mixture of a fluorine-based solvent, an alcohol and an acetate having an alkyl group. In consideration of the solubility of the resist containing the polymer, the combination of the developer and the rinse solution may be, for example, a developer containing a solvent having high solubility in the resist and a rinse solution containing a solvent having low solubility in the resist. In selecting the developing solution, it is preferable to select a developing solution that does not dissolve the resist film before the step (2) is performed. Further, when the rinse liquid is selected, it is preferable to select a rinse liquid that is easily mixed with the developer, so that replacement with the developer is easy.
(method of producing laminate)
The method for producing a laminate according to the present invention is a method for producing a laminate having a substrate, a light-shielding layer formed on the substrate, and a resist film formed on the light-shielding layer, wherein the resist film is formed by the method for forming a resist film according to the present invention.
< substrate >
As the substrate, a transparent substrate is generally used. Examples of the material of the substrate include transparent materials such as quartz and glass. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds. Among them, quartz is preferable from the viewpoint of transparency and weather resistance.
The substrate preferably has transparency such that light having a wavelength of 200nm to 300nm transmits approximately 90% to 95%.
The thickness of the substrate is preferably 0.5mm or more, more preferably 1.0mm or more, preferably 20mm or less, more preferably 15mm or less.
< light-shielding layer >
As the light-shielding layer, an optional light-shielding layer can be used. As the light-shielding layer, a light-shielding layer having a single-layer structure or a multi-layer structure including a metal layer is particularly preferably used. Examples of materials that can constitute the layers other than the metal layer in the light-shielding layer include polypropylene, cyclic polyolefin, and polyvinyl chloride.
Examples of the material of the metal layer include chromium, silicon, iron oxide, molybdenum silicide, and the like. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds. Among them, chromium is preferable from the viewpoint of light-shielding properties.
The thickness of the light-shielding layer is preferably 5nm or more, more preferably 10nm or more, preferably 200nm or less, more preferably 100nm or less.
< resist film >
The resist film is formed by the resist film forming method of the present invention. This improves the adhesion between the resist film and the light-shielding layer, and suppresses the decrease in the molecular weight of the polymer in the resist film.
The thickness of the resist film is preferably 20nm or more, more preferably 30nm or more, preferably 200nm or less, more preferably 100nm or less.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, "%" and "part" of the amounts are based on mass unless otherwise specified.
In fig. 2A to 3E, "circle marks" indicate that (ii) "the retention rate of the weight average molecular weight of the polymer in the resist film formed through the pre-baking step" and (iii) "the adhesion between the resist film formed through the pre-baking step and the workpiece" described later are both good; "cross mark" indicates that either (ii) "retention of polymer weight average molecular weight in the resist film formed through the pre-baking step" or (iii) "adhesion between the resist film formed through the pre-baking step and the workpiece" is not good; the "numerical value" indicated by the arrows pointing to the "circle mark" and the "cross mark" represents the test example number.
In test examples 1-1 to 12-25, (i) "weight average molecular weight, number average molecular weight, and molecular weight distribution", (ii) "retention of polymer weight average molecular weight in a resist film formed through a pre-baking step", and (iii) "adhesion between a resist film formed through a pre-baking step and a workpiece" were measured and evaluated by the following methods, respectively.
< weight average molecular weight, number average molecular weight, and molecular weight distribution >
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer to be measured were measured by a gel permeation chromatograph, and the molecular weight distribution (Mw/Mn) was calculated.
Specifically, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer to be measured were obtained as standard polystyrene conversion values using a gel permeation chromatograph (HLC-8220, manufactured by TOSOH CORPORATION) and tetrahydrofuran as an eluent. Then, the molecular weight distribution (Mw/Mn) was calculated.
< retention of weight average molecular weight of Polymer in resist film formed by Pre-baking Process >
The proportion (%) of the weight average molecular weight of the polymer in the resist film formed through the prebaking step when the weight average molecular weight of the polymer used in the preparation of the positive resist composition was 100% was calculated, and the retention of the weight average molecular weight of the polymer in the resist film formed through the prebaking step was evaluated according to the following criteria.
A: when the weight average molecular weight of the polymer used in the preparation of the positive resist composition is 100%, the proportion of the weight average molecular weight of the polymer in the resist film formed through the prebaking step is 95.7% or more (the retention ratio is large and good)
B: when the weight average molecular weight of the polymer used in the preparation of the positive resist composition is 100%, the proportion of the weight average molecular weight of the polymer in the resist film formed through the prebaking step is less than 95.7% (the retention rate is small)
< adhesion between resist film formed by Pre-baking Process and workpiece >
The formed resist pattern was observed for the presence or absence of peeling, and the adhesion between the resist film and the workpiece was evaluated according to the following criteria.
A: resist pattern peeling-free (good adhesion)
B: resist pattern peeling (adhesion Low)
Example 1
(test example 1-1)
< preparation of Polymer (F5) >
A monomer composition comprising 3.0g of α -chloroacrylic acid-2, 2,3,3, 3-pentafluoropropyl ester (ACAPFP) as a monomer (a) and 3.4764g of α -methylstyrene (AMS) as a monomer (b), 0.0055g of azobisisobutyronitrile as a polymerization initiator, 1.6205g of cyclopentanone as a solvent was charged into a glass vessel, the glass vessel was sealed and nitrogen-substituted, and stirred in a thermostatic bath at 78 ℃ for 6 hours under nitrogen atmosphere, after which it was returned to room temperature, after the inside of the glass vessel was opened to the atmosphere, 10g of Tetrahydrofuran (THF) was added to the resultant solution, then the solution after the addition of THF was added dropwise to 300g of methanol to precipitate a polymerization product, then, the solution containing the precipitated polymerization product was filtered using a hill funnel to obtain a white coagulated product (polymer). next, the resultant polymer (crude product) was dissolved in 100g of THF, the resultant solution was added dropwise to 100g of methanol to 900g of the coagulated product, the white coagulated product (polymer) was filtered using a funnel, and the white coagulated product (polymer) containing a mixed unit of THF, 3-chloropropylene ester, 3-3 mol% precipitated, 3-propylene carbonate unit, and then, 3-propylene carbonate unit was added to obtain a white coagulated polymer (THF-2-3-mole fraction).
Then, the weight average molecular weight, number average molecular weight and molecular weight distribution of the obtained polymer were measured. The measured weight average molecular weight and molecular weight distribution are shown below.
< preparation of Positive resist composition >
The obtained polymer was dissolved in isoamyl acetate as a solvent to prepare a resist solution (positive resist composition) having a polymer concentration of 4 mass%.
< formation of resist Pattern >
A positive resist composition was coated on a mask blank plate having a diameter of 4 inches (a plate having a chromium layer (thickness: 10nm) formed on a quartz substrate (thickness: 1.0 mm)) using a spin coater (MIKASA CO., LTD., MS-A150). Next, the applied positive resist composition was heated for 10 minutes using a hot plate at a temperature of 120 ℃ (prebaking process), and a resist film having a thickness of 50nm was formed on the mask blank. Then, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer in the obtained resist film were measured by a gel permeation chromatograph, and the molecular weight distribution (Mw/Mn) was calculated. In addition, an electron beam drawing device (manufactured by ELIONIX INC., ELS-S50) was used to optimize the exposure dose (E)op) The resist film is exposed to light to draw a pattern. Then, a fluorine-based solvent (Chemours-Mitsui fluoropolymers Co., Ltd., manufactured by Ltd., Vertrel XF (registered trademark), CF, a trade name) was added3CFHCFHCF2CF3) As a developer for resists, a fluorine-based solvent (Chemours-Mitsui fluoropolymers Co., Ltd., manufactured by Ltd.) was used as a rinse solution after a development treatment at 23 ℃ for 1 minute3CFHCFHCF2CF3) For 10 seconds to form a resist pattern. Next, the adhesion between the resist film formed through the prebaking step and the mask blank was evaluated. In addition, the optimum exposure amount (E) is appropriately setop). Further, lines (unexposed regions) and spaces (exposed regions) of the resist pattern were controlled to 20nm, respectively.
< measurement evaluation results >
The evaluation results of the measured weight average molecular weight and molecular weight distribution, the retention rate of the weight average molecular weight, and the adhesion are shown below and in fig. 2A.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 51581, molecular weight distribution: 1.400
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 100.1%, retention rate evaluation result: a (good and high retention)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing)
(test examples 1-2 to 1-21)
Instead of the prebaking step of heating at 120 ℃ for 10 minutes as in test example 1-1, heating at 130 ℃ for 7.5 minutes (test example 1-2), heating at 130 ℃ for 10 minutes (test example 1-3), heating at 140 ℃ for 5 minutes (test example 1-4), heating at 140 ℃ for 7.5 minutes (test example 1-5), heating at 140 ℃ for 10 minutes (test example 1-6), heating at 150 ℃ for 3 minutes (test example 1-7), heating at 150 ℃ for 5 minutes (test example 1-8), heating at 150 ℃ for 7.5 minutes (test example 1-9), heating at 150 ℃ for 10 minutes (test example 1-10), heating at 160 ℃ for 1 minute (test example 1-11), heating at 160 ℃ for 3 minutes (test example 1-12), heating at 160 ℃ for 5 minutes (test example 1-13), and heating at 160 ℃ for 7.5 minutes (test example 1-14) were carried out respectively, The same measurements and evaluations were carried out as in test example 1-1, except for the prebaking step of heating at 160 ℃ for 10 minutes (test examples 1-15), at 170 ℃ for 1 minute (test examples 1-16), at 170 ℃ for 3 minutes (test examples 1-17), at 170 ℃ for 5 minutes (test examples 1-18), at 180 ℃ for 1 minute (test examples 1-19), at 180 ℃ for 3 minutes (test examples 1-20), and at 190 ℃ for 1 minute (test examples 1-21). The results are shown below and in FIG. 2A.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403 (test examples 1-2 to 1-21)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 50877, molecular weight distribution: 1.406 (test examples 1-2)
Weight average molecular weight: 50722, molecular weight distribution: 1.402 (test examples 1-3)
Weight average molecular weight: 50810, molecular weight distribution: 1.404 (test examples 1-4)
Weight average molecular weight: 50462, molecular weight distribution: 1.407 (test examples 1 to 5)
Weight average molecular weight: 50411, molecular weight distribution: 1.410 (test examples 1-6)
Weight average molecular weight: 50914, molecular weight distribution: 1.401 (test examples 1 to 7)
Weight average molecular weight: 50974, molecular weight distribution: 1.412 (test examples 1 to 8)
Weight average molecular weight: 50682, molecular weight distribution: 1.436 (test examples 1 to 9)
Weight average molecular weight: 50509, molecular weight distribution: 1.432 (test examples 1-10)
Weight average molecular weight: 51106, molecular weight distribution: 1.403 (test examples 1 to 11)
Weight average molecular weight: 50679, molecular weight distribution: 1.413 (test examples 1-12)
Weight average molecular weight: 50532, molecular weight distribution: 1.414 (test examples 1-13)
Weight average molecular weight: 50279, molecular weight distribution: 1.417 (test examples 1 to 14)
Weight average molecular weight: 50307, molecular weight distribution: 1.416 (test examples 1-15)
Weight average molecular weight: 51106, molecular weight distribution: 1.403 (test examples 1-16)
Weight average molecular weight: 49767, molecular weight distribution: 1.418 (test examples 1 to 17)
Weight average molecular weight: 50448, molecular weight distribution: 1.415 (test examples 1-18)
Weight average molecular weight: 51106, molecular weight distribution: 1.403 (test examples 1-19)
Weight average molecular weight: 50246, molecular weight distribution: 1.417 (test examples 1-20)
Weight average molecular weight: 51106, molecular weight distribution: 1.403 (test examples 1-21)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 98.7%, retention rate evaluation result: a (good retention ratio) (test examples 1-2)
Retention ratio: 98.4%, retention rate evaluation result: a (good retention ratio) (test examples 1 to 3)
Retention ratio: 98.6%, retention rate evaluation result: a (good retention) (test examples 1 to 4)
Retention ratio: 97.9%, retention rate evaluation result: a (good retention) (test examples 1 to 5)
Retention ratio: 97.8%, retention rate evaluation result: a (good retention ratio) (test examples 1 to 6)
Retention ratio: 98.8%, retention rate evaluation result: a (good retention) (test examples 1 to 7)
Retention ratio: 98.9%, retention rate evaluation result: a (good retention ratio) (test examples 1 to 8)
Retention ratio: 98.4%, retention rate evaluation result: a (good retention) (test examples 1 to 9)
Retention ratio: 98.0%, retention rate evaluation result: a (good retention ratio) (test examples 1 to 10)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 1 to 11)
Retention ratio: 98.4%, retention rate evaluation result: a (good retention) (test examples 1 to 12)
Retention ratio: 98.1%, retention rate evaluation result: a (good retention) (test examples 1 to 13)
Retention ratio: 97.6%, retention rate evaluation result: a (good retention) (test examples 1 to 14)
Retention ratio: 97.6%, retention rate evaluation result: a (good retention ratio) (test examples 1 to 15)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 1 to 16)
Retention ratio: 96.6%, retention rate evaluation result: a (good retention) (test examples 1 to 17)
Retention ratio: 97.9%, retention rate evaluation result: a (good retention) (test examples 1 to 18)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 1 to 19)
Retention ratio: 97.5%, retention rate evaluation result: a (good retention ratio) (test examples 1 to 20)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 1 to 21)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing property) (test examples 1-2 to 1-21)
(test examples 1-22 to 1-26)
The same measurements and evaluations as in test example 1-1 were carried out for "preparation of polymer (F5)", "preparation of positive resist composition", and "formation of resist pattern", except that the prebaking step was carried out for heating at 110 ℃ for 10 minutes (test examples 1 to 22), at 120 ℃ for 7.5 minutes (test examples 1 to 23), at 130 ℃ for 5 minutes (test examples 1 to 24), at 140 ℃ for 3 minutes (test examples 1 to 25), and at 150 ℃ for 1 minute (test examples 1 to 26), respectively, instead of the prebaking step at 120 ℃ for 10 minutes as in test example 1-1. The results are shown below and in FIG. 2A.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403 (test examples 1-22 to 1-26)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 51068, molecular weight distribution: 1.400 (test examples 1-22)
Weight average molecular weight: 51584, molecular weight distribution: 1.400 (test examples 1-23)
Weight average molecular weight: 50668, molecular weight distribution: 1.404 (test examples 1-24)
Weight average molecular weight: 50120, molecular weight distribution: 1.400 (test examples 1-25)
Weight average molecular weight: 51106, molecular weight distribution: 1.403 (test examples 1-26)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 99.1%, retention rate evaluation result: a (good retention) (test examples 1 to 22)
Retention ratio: 100.1%, retention rate evaluation result: a (good retention) (test examples 1 to 23)
Retention ratio: 98.3%, retention rate evaluation result: a (good retention) (test examples 1 to 24)
Retention ratio: 97.3%, retention rate evaluation result: a (good retention) (test examples 1 to 25)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 1 to 26)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: b (Low adhesion) (test examples 1-22 to 1-26)
(test examples 1-27 to 1-30)
"preparation of Polymer (F5)," preparation of Positive resist composition, "and" formation of resist Pattern "were carried out in the same manner as in test example 1-1 except that the prebaking step was carried out at 170 ℃ for 7.5 minutes (test examples 1-27), at 170 ℃ for 10 minutes (test examples 1-28), at 180 ℃ for 5 minutes (test examples 1-29), and at 190 ℃ for 3 minutes (test examples 1-30), instead of the prebaking step at 120 ℃ for 10 minutes carried out in test example 1-1, and the same measurements and evaluations were carried out. The results are shown below and in FIG. 2A.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403 (test examples 1-27 to 1-30)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 48993, molecular weight distribution: 1.437 (test examples 1-27)
Weight average molecular weight: 48632, molecular weight distribution: 1.452 (test examples 1-28)
Weight average molecular weight: 48821, molecular weight distribution: 1.413 (test examples 1-29)
Weight average molecular weight: 48400, molecular weight distribution: 1.437 (test examples 1-30)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 95.1%, retention rate evaluation result: b (maintenance ratio is small) (test examples 1 to 27)
Retention ratio: 94.4%, retention rate evaluation result: b (maintenance ratio is small) (test examples 1 to 28)
Retention ratio: 94.8%, retention rate evaluation result: b (maintenance ratio is small) (test examples 1 to 29)
Retention ratio: 93.9%, retention rate evaluation result: b (maintenance ratio is small) (test examples 1 to 30)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing property) (test examples 1-27 to 1-30)
Example 2
(test example 2-1)
< preparation of Polymer (F6) >
A monomer composition comprising 3.0g of α -chloroacrylic acid-2, 2,3,3, 3-pentafluoropropyl ester (ACAPFP) as a monomer (a) and 3.23483g of 4-fluoro- α -methylstyrene (4FAMS) as a monomer (b), 0.00521g of azobisisobutyronitrile as a polymerization initiator was charged into a glass container, the glass container was sealed and nitrogen-replaced, and stirred in a thermostatic bath at 78 ℃ for 6 hours under nitrogen atmosphere, after which it was returned to room temperature, after the inside of the glass container was opened to the atmosphere, 10g of Tetrahydrofuran (THF) was added to the resulting solution, then the solution to which THF was added dropwise to 300g of methanol to precipitate a polymerization product, then the solution containing the precipitated polymerization product was filtered using tungsan mountain to obtain a white coagulum (polymer). further, the resulting polymer (crude product) was dissolved in 100g of THF, the resulting solution was added dropwise to 50g of THF and 950g of methanol (MeOH), a mixed solvent containing the precipitated white coagulum (polymer) (containing a unit of 393-fluoropropyl ester, a unit of 3-chloropropylene ester, a white coagulated polymer (3-3 mol% and a white coagulated unit of propylene carbonate unit, a coagulated ethylene-3-propylene carbonate unit, 3-propylene unit, 3-propylene carbonate unit, 3-propylene unit, and a white coagulated unit, 3-propylene unit, and a funnel, 3-.
Then, the weight average molecular weight, number average molecular weight and molecular weight distribution of the obtained polymer were measured. The measured weight average molecular weight and molecular weight distribution are shown below.
< preparation of Positive resist composition >
The obtained polymer was dissolved in isoamyl acetate as a solvent to prepare a resist solution (positive resist composition) having a polymer concentration of 4 mass%.
< formation of resist Pattern >
A positive resist composition was coated on a mask blank plate having a diameter of 4 inches (a plate having a chromium layer (thickness: 10nm) formed on a quartz substrate (thickness: 1.0 mm)) using a spin coater (MIKASA CO., LTD., MS-A150). Next, the applied positive resist composition was heated for 10 minutes using a hot plate at a temperature of 120 ℃ (prebaking process), and a resist film having a thickness of 50nm was formed on the mask blank. Then, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer in the obtained resist film were measured by a gel permeation chromatograph, and the molecular weight distribution (Mw/Mn) was calculated. In addition, an electron beam drawing device (manufactured by ELIONIX INC., ELS-S50) was used to optimize the exposure dose (E)op) The resist film is exposed to light to draw a pattern. Then, a fluorine-based solvent (Chemours-Mitsui fluoropolymers Co., Ltd., manufactured by Ltd., Vertrel XF (registered trademark), CF, a trade name) was added3CFHCFHCF2CF3) As a developer for resists, a fluorine-based solvent (Chemours-Mitsui fluoropolymers Co., Ltd., manufactured by Ltd.) was used as a rinse solution after a development treatment at 23 ℃ for 1 minute3CFHCFHCF2CF3) For 10 seconds to form a resist pattern. Next, the adhesion between the resist film formed through the prebaking step and the mask blank was evaluated. In addition, the optimum exposure amount (E) is appropriately setop). Further, lines (unexposed regions) and spaces (exposed regions) of the resist patternRegions) were controlled to 20nm, respectively.
< measurement evaluation results >
The evaluation results of the measured weight average molecular weight and molecular weight distribution, the retention rate of the weight average molecular weight, and the adhesion are shown below and in fig. 3A.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 48511, molecular weight distribution: 1.283
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 102.5%, retention rate evaluation result: a (good and high retention)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing)
(test examples 2-2 to 2-29)
Instead of the prebaking step of heating at 120 ℃ for 10 minutes as in test example 2-1, heating at 130 ℃ for 7.5 minutes (test example 2-2), heating at 130 ℃ for 10 minutes (test example 2-3), heating at 140 ℃ for 5 minutes (test example 2-4), heating at 140 ℃ for 7.5 minutes (test example 2-5), heating at 140 ℃ for 10 minutes (test example 2-6), heating at 150 ℃ for 3 minutes (test example 2-7), heating at 150 ℃ for 5 minutes (test example 2-8), heating at 150 ℃ for 7.5 minutes (test example 2-9), heating at 150 ℃ for 10 minutes (test example 2-10), heating at 160 ℃ for 1 minute (test example 2-11), heating at 160 ℃ for 3 minutes (test example 2-12), heating at 160 ℃ for 5 minutes (test example 2-13), and heating at 160 ℃ for 7.5 minutes (test example 2-14) were carried out respectively, A pre-baking step of heating at 160 ℃ for 10 minutes (test examples 2 to 15), at 170 ℃ for 1 minute (test examples 2 to 16), at 170 ℃ for 3 minutes (test examples 2 to 17), at 170 ℃ for 5 minutes (test examples 2 to 18), at 170 ℃ for 7.5 minutes (test examples 2 to 19), at 170 ℃ for 10 minutes (test examples 2 to 20), at 180 ℃ for 1 minute (test examples 2 to 21), at 180 ℃ for 3 minutes (test examples 2 to 22), at 180 ℃ for 5 minutes (test examples 2 to 23), at 180 ℃ for 7.5 minutes (test examples 2 to 24), at 180 ℃ for 10 minutes (test examples 2 to 25), at 190 ℃ for 1 minute (test examples 2 to 26), at 190 ℃ for 3 minutes (test examples 2 to 27), at 190 ℃ for 5 minutes (test examples 2 to 28), and at 190 ℃ for 7.5 minutes (test examples 2 to 29), except for this, the same measurements and evaluations as in test example 2-1 were carried out for "production of polymer (F6)", "production of positive resist composition", and "formation of resist pattern". The results are shown below and in FIG. 3A.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284 (test examples 2-2 to 2-29)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 48583, molecular weight distribution: 1.285 (test example 2-2)
Weight average molecular weight: 48511, molecular weight distribution: 1.282 (test examples 2 to 3)
Weight average molecular weight: 48111, molecular weight distribution: 1.283 (test examples 2-4)
Weight average molecular weight: 47610, molecular weight distribution: 1.285 (test examples 2-5)
Weight average molecular weight: 47351, molecular weight distribution: 1.284 (test examples 2-6)
Weight average molecular weight: 47974, molecular weight distribution: 1.288 (test examples 2-7)
Weight average molecular weight: 48381 molecular weight distribution: 1.285 (test examples 2-8)
Weight average molecular weight: 47692, molecular weight distribution: 1.288 (test examples 2-9)
Weight average molecular weight: 47829, molecular weight distribution: 1.291 (test examples 2-10)
Weight average molecular weight: 46929, molecular weight distribution: 1.284 (test examples 2 to 11)
Weight average molecular weight: 47739, molecular weight distribution: 1.282 (test examples 2 to 12)
Weight average molecular weight: 47968, molecular weight distribution: 1.288 (test examples 2-13)
Weight average molecular weight: 47262, molecular weight distribution: 1.292 (test examples 2 to 14)
Weight average molecular weight: 47068, molecular weight distribution: 1.300 (test examples 2-15)
Weight average molecular weight: 46929, molecular weight distribution: 1.284 (test examples 2-16)
Weight average molecular weight: 46900, molecular weight distribution: 1.284 (test examples 2-17)
Weight average molecular weight: 47754, molecular weight distribution: 1.293 (test examples 2-18)
Weight average molecular weight: 46746, molecular weight distribution: 1.302 (test examples 2-19)
Weight average molecular weight: 47502, molecular weight distribution: 1.313 (test examples 2-20)
Weight average molecular weight: 46929, molecular weight distribution: 1.284 (test examples 2-21)
Weight average molecular weight: 47730, molecular weight distribution: 1.291 (test examples 2-22)
Weight average molecular weight: 47275, molecular weight distribution: 1.301 (test examples 2-23)
Weight average molecular weight: 45765, molecular weight distribution: 1.318 (test examples 2 to 24)
Weight average molecular weight: 45769, molecular weight distribution: 1.317 (test examples 2-25)
Weight average molecular weight: 46929, molecular weight distribution: 1.284 (test examples 2-26)
Weight average molecular weight: 47656, molecular weight distribution: 1.299 (test examples 2-27)
Weight average molecular weight: 46846, molecular weight distribution: 1.306 (test examples 2 to 28)
Weight average molecular weight: 45478, molecular weight distribution: 1.318 (test examples 2 to 29)
(iii) Retention of weight average molecular weight of polymer in resist film formed via prebaking process
Retention ratio: 102.7%, retention rate evaluation result: a (good retention ratio) (test example 2-2)
Retention ratio: 102.5%, retention rate evaluation result: a (good retention ratio) (test examples 2 to 3)
Retention ratio: 101.7%, retention rate evaluation result: a (good retention ratio) (test examples 2 to 4)
Retention ratio: 100.6%, retention rate evaluation result: a (good retention) (test examples 2 to 5)
Retention ratio: 100.1%, retention rate evaluation result: a (good retention ratio) (test examples 2 to 6)
Retention ratio: 101.4%, retention rate evaluation result: a (good retention) (test examples 2 to 7)
Retention ratio: 102.3%, retention rate evaluation result: a (good retention ratio) (test examples 2 to 8)
Retention ratio: 100.8%, retention rate evaluation result: a (good retention) (test examples 2 to 9)
Retention ratio: 101.1%, retention rate evaluation result: a (good retention ratio) (test examples 2 to 10)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 2 to 11)
Retention ratio: 100.9%, retention rate evaluation result: a (good retention) (test examples 2 to 12)
Retention ratio: 101.4%, retention rate evaluation result: a (good retention) (test examples 2 to 13)
Retention ratio: 99.9%, retention rate evaluation result: a (good retention) (test examples 2 to 14)
Retention ratio: 99.5%, retention rate evaluation result: a (good retention ratio) (test examples 2 to 15)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 2 to 16)
Retention ratio: 99.1%, retention rate evaluation result: a (good retention) (test examples 2 to 17)
Retention ratio: 100.9%, retention rate evaluation result: a (good retention ratio) (test examples 2 to 18)
Retention ratio: 98.8%, retention rate evaluation result: a (good retention) (test examples 2 to 19)
Retention ratio: 98.3%, retention rate evaluation result: a (good retention ratio) (test examples 2 to 20)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 2 to 21)
Retention ratio: 100.9%, retention rate evaluation result: a (good retention) (test examples 2 to 22)
Retention ratio: 99.9%, retention rate evaluation result: a (good retention) (test examples 2 to 23)
Retention ratio: 96.7%, retention rate evaluation result: a (good retention) (test examples 2 to 24)
Retention ratio: 96.7%, retention rate evaluation result: a (good retention) (test examples 2 to 25)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 2 to 26)
Retention ratio: 100.7%, retention rate evaluation result: a (good retention) (test examples 2 to 27)
Retention ratio: 99.0%, retention rate evaluation result: a (good retention) (test examples 2 to 28)
Retention ratio: 96.1%, retention rate evaluation result: a (good retention) (test examples 2 to 29)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing property) (test examples 2-2 to 2-29)
(test examples 2-30 to 2-34)
The same measurements and evaluations as in test example 2-1 were carried out for "preparation of polymer (F6)", "preparation of positive resist composition", and "formation of resist pattern", except that the prebaking step was carried out for heating at 110 ℃ for 10 minutes (test examples 2 to 30), at 120 ℃ for 7.5 minutes (test examples 2 to 31), at 130 ℃ for 5 minutes (test examples 2 to 32), at 140 ℃ for 3 minutes (test examples 2 to 33), and at 150 ℃ for 1 minute (test examples 2 to 34), respectively, instead of the prebaking step at 120 ℃ for 10 minutes carried out in test example 2-1. The results are shown below and in FIG. 3A.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284 (test examples 2-30 to 2-34)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 48511, molecular weight distribution: 1.283 (test examples 2-30)
Weight average molecular weight: 48564 molecular weight distribution: 1.286 (test examples 2 to 31)
Weight average molecular weight: 47869, molecular weight distribution: 1.276 (test examples 2-32)
Weight average molecular weight: 47271, molecular weight distribution: 1.285 (test examples 2-33)
Weight average molecular weight: 46929, molecular weight distribution: 1.284 (test examples 2-34)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 102.5%, retention rate evaluation result: a (good retention) (test examples 2 to 30)
Retention ratio: 102.6%, retention rate evaluation result: a (good retention) (test examples 2 to 31)
Retention ratio: 101.2%, retention rate evaluation result: a (good retention) (test examples 2 to 32)
Retention ratio: 99.9%, retention rate evaluation result: a (good retention) (test examples 2 to 33)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 2 to 34)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: b (Low adhesion) (test examples 2-30 to 2-34)
(test examples 2 to 35)
The same measurements and evaluations were carried out as in test example 2-1 except that "preparation of polymer (F6)", "preparation of positive resist composition", "formation of resist pattern" and the like were carried out in the same manner as in test example 2-1, except that the prebaking step of heating at 120 ℃ for 10 minutes and the prebaking step of heating at 190 ℃ for 10 minutes were carried out instead of the prebaking step carried out in test example 2-1. The results are shown below and in FIG. 3A.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 45087, molecular weight distribution: 1.323
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 95.3%, retention rate evaluation result: b (retention rate is small)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing)
Example 3
(test example 3-1)
"preparation of Polymer (F5)," preparation of Positive resist composition, "and" formation of resist Pattern "were carried out in the same manner as in test example 1-1 except that n-butyl formate was used instead of isoamyl acetate used in test example 1-1 and that a prebaking step was carried out at 100 ℃ for 10 minutes instead of the prebaking step at 120 ℃ for 10 minutes. The results are shown below and in FIG. 2B.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 51701, molecular weight distribution: 1.400
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 100.3%, retention rate evaluation result: a (good and high retention)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing)
(test examples 3-2 to 3-31)
Instead of the prebaking step of heating at 100 ℃ for 10 minutes as in test example 3-1, heating at 110 ℃ for 7.5 minutes (test example 3-2), heating at 110 ℃ for 10 minutes (test example 3-3), heating at 120 ℃ for 5 minutes (test example 3-4), heating at 120 ℃ for 7.5 minutes (test example 3-5), heating at 120 ℃ for 10 minutes (test example 3-6), heating at 130 ℃ for 3 minutes (test example 3-7), heating at 130 ℃ for 5 minutes (test example 3-8), heating at 130 ℃ for 7.5 minutes (test example 3-9), heating at 130 ℃ for 10 minutes (test example 3-10), heating at 140 ℃ for 1 minute (test example 3-11), heating at 140 ℃ for 3 minutes (test example 3-12), heating at 140 ℃ for 5 minutes (test example 3-13), and heating at 140 ℃ for 7.5 minutes (test example 3-14) were carried out, Heating at 140 ℃ for 10 minutes (examples 3 to 15), heating at 150 ℃ for 1 minute (examples 3 to 16), heating at 150 ℃ for 3 minutes (examples 3 to 17), heating at 150 ℃ for 5 minutes (examples 3 to 18), heating at 150 ℃ for 7.5 minutes (examples 3 to 19), heating at 150 ℃ for 10 minutes (examples 3 to 20), heating at 160 ℃ for 1 minute (examples 3 to 21), heating at 160 ℃ for 3 minutes (examples 3 to 22), heating at 160 ℃ for 5 minutes (examples 3 to 23), heating at 160 ℃ for 7.5 minutes (examples 3 to 24), heating at 160 ℃ for 10 minutes (examples 3 to 25), heating at 170 ℃ for 1 minute (examples 3 to 26), heating at 170 ℃ for 3 minutes (examples 3 to 27), heating at 170 ℃ for 5 minutes (examples 3 to 28), and heating at 180 ℃ for 1 minute (examples 3 to 29), The same measurements and evaluations were carried out as in test example 3-1, except for the prebaking step of heating at 180 ℃ for 3 minutes (test examples 3-30) and heating at 190 ℃ for 1 minute (test examples 3-31), "preparation of polymer (F5)," preparation of positive resist composition "and" formation of resist pattern ". The results are shown below and in fig. 2B.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403 (test examples 3-2 to 3-31)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 51693, molecular weight distribution: 1.400 (test example 3-2)
Weight average molecular weight: 51701, molecular weight distribution: 1.400 (test 3-3)
Weight average molecular weight: 51352, molecular weight distribution: 1.400 (test examples 3-4)
Weight average molecular weight: 51693, molecular weight distribution: 1.400 (test examples 3-5)
Weight average molecular weight: 51701, molecular weight distribution: 1.400 (test examples 3-6)
Weight average molecular weight: 50919, molecular weight distribution: 1.404 (test examples 3-7)
Weight average molecular weight: 50621, molecular weight distribution: 1.406 (test examples 3 to 8)
Weight average molecular weight: 50985, molecular weight distribution: 1.406 (test examples 3 to 9)
Weight average molecular weight: 50839, molecular weight distribution: 1.403 (test examples 3-10)
Weight average molecular weight: 51125, molecular weight distribution: 1.400 (test examples 3-11)
Weight average molecular weight: 50125, molecular weight distribution: 1.404 (test examples 3-12)
Weight average molecular weight: 50763, molecular weight distribution: 1.407 (test examples 3-13)
Weight average molecular weight: 50569, molecular weight distribution: 1.407 (test examples 3-14)
Weight average molecular weight: 50528, molecular weight distribution: 1.405 (test examples 3 to 15)
Weight average molecular weight: 51125, molecular weight distribution: 1.401 (test examples 3 to 16)
Weight average molecular weight: 50919, molecular weight distribution: 1.412 (test examples 3-17)
Weight average molecular weight: 50926, molecular weight distribution: 1.436 (test examples 3-18)
Weight average molecular weight: 50790, molecular weight distribution: 1.436 (test examples 3 to 19)
Weight average molecular weight: 50626, molecular weight distribution: 1.416 (test examples 3-20)
Weight average molecular weight: 51125, molecular weight distribution: 1.413 (test examples 3-21)
Weight average molecular weight: 50684, molecular weight distribution: 1.414 (test examples 3-22)
Weight average molecular weight: 50485, molecular weight distribution: 1.417 (test examples 3-23)
Weight average molecular weight: 50386, molecular weight distribution: 1.417 (test examples 3-24)
Weight average molecular weight: 50424, molecular weight distribution: 1.422 (test examples 3-25)
Weight average molecular weight: 51125, molecular weight distribution: 1.418 (test examples 3-26)
Weight average molecular weight: 49772, molecular weight distribution: 1.415 (test examples 3-27)
Weight average molecular weight: 50400, molecular weight distribution: 1.437 (test examples 3-28)
Weight average molecular weight: 51125, molecular weight distribution: 1.417 (test examples 3-29)
Weight average molecular weight: 50251, molecular weight distribution: 1.448 (test examples 3-30)
Weight average molecular weight: 51125, molecular weight distribution: 1.437 (test examples 3-31)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 100.3%, retention rate evaluation result: a (good retention ratio) (test example 3-2)
Retention ratio: 100.3%, retention rate evaluation result: a (good retention) (test examples 3-3)
Retention ratio: 99.7%, retention rate evaluation result: a (good retention) (test examples 3 to 4)
Retention ratio: 100.3%, retention rate evaluation result: a (good retention) (test examples 3 to 5)
Retention ratio: 100.3%, retention rate evaluation result: a (good retention) (test examples 3 to 6)
Retention ratio: 98.8%, retention rate evaluation result: a (good retention) (test examples 3 to 7)
Retention ratio: 98.3%, retention rate evaluation result: a (good retention) (test examples 3 to 8)
Retention ratio: 99.0%, retention rate evaluation result: a (good retention) (test examples 3 to 9)
Retention ratio: 98.7%, retention rate evaluation result: a (good retention) (test examples 3 to 10)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 3 to 11)
Retention ratio: 97.3%, retention rate evaluation result: a (good retention) (test examples 3 to 12)
Retention ratio: 98.5%, retention rate evaluation result: a (good retention) (test examples 3 to 13)
Retention ratio: 98.2%, retention rate evaluation result: a (good retention) (test examples 3 to 14)
Retention ratio: 98.1%, retention rate evaluation result: a (good retention) (test examples 3 to 15)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 3 to 16)
Retention ratio: 98.8%, retention rate evaluation result: a (good retention) (test examples 3 to 17)
Retention ratio: 98.8%, retention rate evaluation result: a (good retention) (test examples 3 to 18)
Retention ratio: 98.6%, retention rate evaluation result: a (good retention) (test examples 3 to 19)
Retention ratio: 98.3%, retention rate evaluation result: a (good retention ratio) (test examples 3 to 20)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 3 to 21)
Retention ratio: 98.4%, retention rate evaluation result: a (good retention) (test examples 3 to 22)
Retention ratio: 98.0%, retention rate evaluation result: a (good retention) (test examples 3 to 23)
Retention ratio: 97.8%, retention rate evaluation result: a (good retention) (test examples 3 to 24)
Retention ratio: 97.9%, retention rate evaluation result: a (good retention) (test examples 3 to 25)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 3 to 26)
Retention ratio: 96.6%, retention rate evaluation result: a (good retention) (test examples 3 to 27)
Retention ratio: 97.8%, retention rate evaluation result: a (good retention) (test examples 3 to 28)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 3 to 29)
Retention ratio: 97.5%, retention rate evaluation result: a (good retention) (test examples 3 to 30)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 3 to 31)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing property) (test examples 3-2 to 3-31)
(test examples 3-32 to 3-36)
The same measurements and evaluations as in test example 3-1 were carried out for "preparation of polymer (F5)", "preparation of positive resist composition", and "formation of resist pattern" except that, instead of the prebaking step of heating at 100 ℃ for 10 minutes as in test example 3-1, the prebaking steps of heating at 90 ℃ for 10 minutes (test examples 3-32), heating at 100 ℃ for 7.5 minutes (test examples 3-33), heating at 110 ℃ for 5 minutes (test examples 3-34), heating at 120 ℃ for 3 minutes (test examples 3-35), and heating at 130 ℃ for 1 minute (test examples 3-36) were carried out, respectively. The results are shown below and in FIG. 2B.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403 (test examples 3-32 to 3-36)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 51701, molecular weight distribution: 1.400 (test examples 3-32)
Weight average molecular weight: 51693, molecular weight distribution: 1.400 (test examples 3-33)
Weight average molecular weight: 51352, molecular weight distribution: 1.400 (test examples 3-34)
Weight average molecular weight: 51185, molecular weight distribution: 1.402 (test examples 3-35)
Weight average molecular weight: 51125, molecular weight distribution: 1.404 (test examples 3-36)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 100.3%, retention rate evaluation result: a (good retention) (test examples 3 to 32)
Retention ratio: 100.3%, retention rate evaluation result: a (good retention) (test examples 3 to 33)
Retention ratio: 99.7%, retention rate evaluation result: a (good retention) (test examples 3 to 34)
Retention ratio: 99.3%, retention rate evaluation result: a (good retention) (test examples 3 to 35)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 3 to 36)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: b (Low adhesion) (test examples 3-32 to 3-36)
(test examples 3-37 to 3-40)
"preparation of Polymer (F5)," preparation of Positive resist composition, "and" formation of resist Pattern "were carried out in the same manner as in test example 3-1 except that the prebaking step was carried out at 170 ℃ for 7.5 minutes (test examples 3-37), at 170 ℃ for 10 minutes (test examples 3-38), at 180 ℃ for 5 minutes (test examples 3-39), and at 190 ℃ for 3 minutes (test examples 3-40), respectively, instead of the prebaking step at 100 ℃ for 10 minutes carried out in test example 3-1. The results are shown below and in FIG. 2B.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403 (test examples 3-37 to 3-40)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 49097 molecular weight distribution: 1.437 (test examples 3-37)
Weight average molecular weight: 48745, molecular weight distribution: 1.451 (test examples 3-38)
Weight average molecular weight: 47836, molecular weight distribution: 1.456 (test examples 3-39)
Weight average molecular weight: 48405, molecular weight distribution: 1.462 (test examples 3-40)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 95.3%, retention rate evaluation result: b (maintenance ratio is small) (test examples 3 to 37)
Retention ratio: 94.6%, retention rate evaluation result: b (maintenance ratio is small) (test examples 3 to 38)
Retention ratio: 92.8%, retention rate evaluation result: b (maintenance ratio is small) (test examples 3 to 39)
Retention ratio: 93.9%, retention rate evaluation result: b (retention ratio is small) (test examples 3 to 40)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing property) (test examples 3-37 to 3-40)
Example 4
(test example 4-1)
"preparation of Polymer (F6)," preparation of Positive resist composition, "and" formation of resist Pattern "were carried out in the same manner as in test example 2-1 except that n-butyl formate was used instead of isoamyl acetate used in test example 2-1 and that a prebaking step was carried out at 100 ℃ for 10 minutes instead of the prebaking step at 120 ℃ for 10 minutes. The results are shown below and in FIG. 3B.
< measurement evaluation results >
The evaluation results of the measured weight average molecular weight and molecular weight distribution, weight average molecular weight retention ratio, and adhesion are shown below and in fig. 3B.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 48624, molecular weight distribution: 1.283
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 102.8%, retention rate evaluation result: a (good and high retention)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing)
(test examples 4-2 to 4-39)
Instead of the prebaking step of heating at 100 ℃ for 10 minutes as in test example 4-1, heating at 110 ℃ for 7.5 minutes (test example 4-2), heating at 110 ℃ for 10 minutes (test example 4-3), heating at 120 ℃ for 5 minutes (test example 4-4), heating at 120 ℃ for 7.5 minutes (test example 4-5), heating at 120 ℃ for 10 minutes (test example 4-6), heating at 130 ℃ for 3 minutes (test example 4-7), heating at 130 ℃ for 5 minutes (test example 4-8), heating at 130 ℃ for 7.5 minutes (test example 4-9), heating at 130 ℃ for 10 minutes (test example 4-10), heating at 140 ℃ for 1 minute (test example 4-11), heating at 140 ℃ for 3 minutes (test example 4-12), heating at 140 ℃ for 5 minutes (test example 4-13), and heating at 140 ℃ for 7.5 minutes (test example 4-14) were carried out, Heating at 140 ℃ for 10 minutes (examples 4 to 15), heating at 150 ℃ for 1 minute (examples 4 to 16), heating at 150 ℃ for 3 minutes (examples 4 to 17), heating at 150 ℃ for 5 minutes (examples 4 to 18), heating at 150 ℃ for 7.5 minutes (examples 4 to 19), heating at 150 ℃ for 10 minutes (examples 4 to 20), heating at 160 ℃ for 1 minute (examples 4 to 21), heating at 160 ℃ for 3 minutes (examples 4 to 22), heating at 160 ℃ for 5 minutes (examples 4 to 23), heating at 160 ℃ for 7.5 minutes (examples 4 to 24), heating at 160 ℃ for 10 minutes (examples 4 to 25), heating at 170 ℃ for 1 minute (examples 4 to 26), heating at 170 ℃ for 3 minutes (examples 4 to 27), heating at 170 ℃ for 5 minutes (examples 4 to 28), and heating at 170 ℃ for 7.5 minutes (examples 4 to 29), The same measurements and evaluations were carried out as in test example 4-1 except for the prebaking step of heating at 170 ℃ for 10 minutes (test examples 4-30), heating at 180 ℃ for 1 minute (test examples 4-31), heating at 180 ℃ for 3 minutes (test examples 4-32), heating at 180 ℃ for 5 minutes (test examples 4-33), heating at 180 ℃ for 7.5 minutes (test examples 4-34), heating at 180 ℃ for 10 minutes (test examples 4-35), heating at 190 ℃ for 1 minute (test examples 4-36), heating at 190 ℃ for 3 minutes (test examples 4-37), heating at 190 ℃ for 5 minutes (test examples 4-38), and heating at 190 ℃ for 7.5 minutes (test examples 4-39). The results are shown below and in FIG. 3B.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284 (test example 4-2 to 4-39)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 48667, molecular weight distribution: 1.286 (test example 4-2)
Weight average molecular weight: 48624, molecular weight distribution: 1.283 (test 4-3)
Weight average molecular weight: 48622, molecular weight distribution: 1.288 (test 4-4)
Weight average molecular weight: 48667, molecular weight distribution: 1.286 (test examples 4 to 5)
Weight average molecular weight: 48624, molecular weight distribution: 1.283 (test examples 4-6)
Weight average molecular weight: 47276, molecular weight distribution: 1.289 (test examples 4-7)
Weight average molecular weight: 47824, molecular weight distribution: 1.276 (test examples 4-8)
Weight average molecular weight: 48686 molecular weight distribution: 1.285 (test examples 4-9)
Weight average molecular weight: 48624, molecular weight distribution: 1.282 (test examples 4 to 10)
Weight average molecular weight: 46947, molecular weight distribution: 1.284 (test examples 4 to 11)
Weight average molecular weight: 47276, molecular weight distribution: 1.285 (test examples 4-12)
Weight average molecular weight: 48066, molecular weight distribution: 1.283 (test examples 4-13)
Weight average molecular weight: 47711, molecular weight distribution: 1.285 (test examples 4-14)
Weight average molecular weight: 47461, molecular weight distribution: 1.284 (test examples 4 to 15)
Weight average molecular weight: 46947, molecular weight distribution: 1.284 (test examples 4-16)
Weight average molecular weight: 47979, molecular weight distribution: 1.288 (test examples 4-17)
Weight average molecular weight: 48335, molecular weight distribution: 1.285 (test examples 4-18)
Weight average molecular weight: 47793, molecular weight distribution: 1.288 (test examples 4-19)
Weight average molecular weight: 47940, molecular weight distribution: 1.291 (test examples 4-20)
Weight average molecular weight: 46947, molecular weight distribution: 1.284 (test examples 4 to 21)
Weight average molecular weight: 47744, molecular weight distribution: 1.282 (test examples 4 to 22)
Weight average molecular weight: 47923 molecular weight distribution: 1.288 (test 4-23)
Weight average molecular weight: 47362, molecular weight distribution: 1.292 (test examples 4 to 24)
Weight average molecular weight: 47177, molecular weight distribution: 1.300 (test examples 4-25)
Weight average molecular weight: 46947, molecular weight distribution: 1.284 (test examples 4 to 26)
Weight average molecular weight: 46905, molecular weight distribution: 1.284 (test examples 4 to 27)
Weight average molecular weight: 47709, molecular weight distribution: 1.293 (test examples 4-28)
Weight average molecular weight: 46845, molecular weight distribution: 1.302 (test examples 4-29)
Weight average molecular weight: 46610, molecular weight distribution: 1.313 (test examples 4-30)
Weight average molecular weight: 46947, molecular weight distribution: 1.284 (test examples 4-31)
Weight average molecular weight: 47734, molecular weight distribution: 1.291 (test examples 4-32)
Weight average molecular weight: 47231, molecular weight distribution: 1.301 (test examples 4-33)
Weight average molecular weight: 45862, molecular weight distribution: 1.318 (test examples 4 to 34)
Weight average molecular weight: 45875, molecular weight distribution: 1.317 (test examples 4-35)
Weight average molecular weight: 46947, molecular weight distribution: 1.284 (test examples 4 to 36)
Weight average molecular weight: 47661, molecular weight distribution: 1.299 (test examples 4-37)
Weight average molecular weight: 46802, molecular weight distribution: 1.306 (test examples 4-38)
Weight average molecular weight: 45574, molecular weight distribution: 1.318 (test examples 4-39)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 102.9%, retention rate evaluation result: a (good retention ratio) (test example 4-2)
Retention ratio: 102.8%, retention rate evaluation result: a (good retention) (test examples 4-3)
Retention ratio: 102.8%, retention rate evaluation result: a (good retention) (test examples 4-4)
Retention ratio: 102.9%, retention rate evaluation result: a (good retention) (test examples 4 to 5)
Retention ratio: 102.8%, retention rate evaluation result: a (good retention) (test examples 4 to 6)
Retention ratio: 99.9%, retention rate evaluation result: a (good retention) (test examples 4 to 7)
Retention ratio: 101.1%, retention rate evaluation result: a (good retention) (test examples 4 to 8)
Retention ratio: 102.9%, retention rate evaluation result: a (good retention) (test examples 4 to 9)
Retention ratio: 102.8%, retention rate evaluation result: a (good retention) (test examples 4 to 10)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 4 to 11)
Retention ratio: 99.9%, retention rate evaluation result: a (good retention) (test examples 4 to 12)
Retention ratio: 101.6%, retention rate evaluation result: a (good retention) (test examples 4 to 13)
Retention ratio: 100.8%, retention rate evaluation result: a (good retention) (test examples 4 to 14)
Retention ratio: 100.3%, retention rate evaluation result: a (good retention) (test examples 4 to 15)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 4 to 16)
Retention ratio: 101.4%, retention rate evaluation result: a (good retention) (test examples 4 to 17)
Retention ratio: 102.2%, retention rate evaluation result: a (good retention) (test examples 4 to 18)
Retention ratio: 101.0%, retention rate evaluation result: a (good retention) (test examples 4 to 19)
Retention ratio: 101.3%, retention rate evaluation result: a (good retention ratio) (test examples 4 to 20)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 4 to 21)
Retention ratio: 100.9%, retention rate evaluation result: a (good retention) (test examples 4 to 22)
Retention ratio: 101.3%, retention rate evaluation result: a (good retention) (test examples 4 to 23)
Retention ratio: 100.1%, retention rate evaluation result: a (good retention) (test examples 4 to 24)
Retention ratio: 99.7%, retention rate evaluation result: a (good retention) (test examples 4 to 25)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 4 to 26)
Retention ratio: 99.1%, retention rate evaluation result: a (good retention) (test examples 4 to 27)
Retention ratio: 100.8%, retention rate evaluation result: a (good retention) (test examples 4 to 28)
Retention ratio: 99.0%, retention rate evaluation result: a (good retention) (test examples 4 to 29)
Retention ratio: 98.5%, retention rate evaluation result: a (good retention) (test examples 4 to 30)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 4 to 31)
Retention ratio: 100.9%, retention rate evaluation result: a (good retention) (test examples 4 to 32)
Retention ratio: 99.8%, retention rate evaluation result: a (good retention) (test examples 4 to 33)
Retention ratio: 96.9%, retention rate evaluation result: a (good retention) (test examples 4 to 34)
Retention ratio: 97.0%, retention rate evaluation result: a (good retention) (test examples 4 to 35)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 4 to 36)
Retention ratio: 100.7%, retention rate evaluation result: a (good retention) (test examples 4 to 37)
Retention ratio: 98.9%, retention rate evaluation result: a (good retention) (test examples 4 to 38)
Retention ratio: 96.3%, retention rate evaluation result: a (good retention) (test examples 4 to 39)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing property) (test examples 4-2 to 4-39)
(test examples 4-40 to 4-44)
The same measurements and evaluations as in test example 4-1 were carried out for "preparation of polymer (F6)", "preparation of positive resist composition", and "formation of resist pattern", except that the prebaking step was carried out for heating at 90 ℃ for 10 minutes (test examples 4 to 40), at 100 ℃ for 7.5 minutes (test examples 4 to 41), at 110 ℃ for 5 minutes (test examples 4 to 42), at 120 ℃ for 3 minutes (test examples 4 to 43), and at 130 ℃ for 1 minute (test examples 4 to 44), respectively, instead of the prebaking step at 100 ℃ for 10 minutes as in test example 4-1. The results are shown below and in FIG. 3B.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 48624, molecular weight distribution: 1.283 (test examples 4-40)
Weight average molecular weight: 48667, molecular weight distribution: 1.286 (test examples 4-41)
Weight average molecular weight: 48622, molecular weight distribution: 1.288 (test examples 4-42)
Weight average molecular weight: 47044, molecular weight distribution: 1.285 (test examples 4-43)
Weight average molecular weight: 46947, molecular weight distribution: 1.284 (test examples 4-44)
(iii) Retention of weight average molecular weight of polymer in resist film formed via prebaking process
Retention ratio: 102.8%, retention rate evaluation result: a (good retention) (test examples 4-40)
Retention ratio: 102.9%, retention rate evaluation result: a (good retention) (test examples 4-41)
Retention ratio: 102.8%, retention rate evaluation result: a (good retention) (test examples 4 to 42)
Retention ratio: 99.4%, retention rate evaluation result: a (good retention) (test examples 4 to 43)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 4 to 44)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: b (Low adhesion) (test examples 4-40 to 4-44)
(test examples 4 to 45)
"preparation of Polymer (F6)," preparation of Positive resist composition "and" formation of resist Pattern "were carried out in the same manner as in test example 4-1 except that the prebaking step of heating at 100 ℃ for 10 minutes and the prebaking step of heating at 190 ℃ for 10 minutes were carried out in place of the prebaking step of heating at 100 ℃ for 10 minutes carried out in test example 4-1, and the same measurements and evaluations were carried out. The results are shown below and in FIG. 3B.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 45191, molecular weight distribution: 1.323
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 95.5%, retention rate evaluation result: b (retention rate is small)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing)
Example 5
(test example 5-1)
"preparation of Polymer (F5)," preparation of Positive resist composition, "and" formation of resist Pattern "were carried out in the same manner as in test example 1-1 except that isobutyl formate was used instead of isoamyl acetate used in test example 1-1, and a prebaking step was carried out by heating at 90 ℃ for 10 minutes instead of the prebaking step by heating at 120 ℃ for 10 minutes. The results are shown below and in fig. 2C.
< measurement evaluation results >
The evaluation results of the measured weight average molecular weight and molecular weight distribution, weight average molecular weight retention rate, and adhesion are shown below and in fig. 2C.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 51685, molecular weight distribution: 1.400
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 100.3%, retention rate evaluation result: a (good and high retention)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing)
(test example 5-2 to test example 5-36)
Instead of the prebaking step of heating at 90 ℃ for 10 minutes as in test example 5-1, heating at 100 ℃ for 7.5 minutes (test example 5-2), heating at 100 ℃ for 10 minutes (test example 5-3), heating at 110 ℃ for 5 minutes (test example 5-4), heating at 110 ℃ for 7.5 minutes (test example 5-5), heating at 110 ℃ for 10 minutes (test example 5-6), heating at 120 ℃ for 3 minutes (test example 5-7), heating at 120 ℃ for 5 minutes (test example 5-8), heating at 120 ℃ for 7.5 minutes (test example 5-9), heating at 120 ℃ for 10 minutes (test example 5-10), heating at 130 ℃ for 1 minute (test example 5-11), heating at 130 ℃ for 3 minutes (test example 5-12), heating at 130 ℃ for 5 minutes (test example 5-13), and heating at 130 ℃ for 7.5 minutes (test example 5-14) were carried out, Heating at 130 ℃ for 10 minutes (examples 5 to 15), heating at 140 ℃ for 1 minute (examples 5 to 16), heating at 140 ℃ for 3 minutes (examples 5 to 17), heating at 140 ℃ for 5 minutes (examples 5 to 18), heating at 140 ℃ for 7.5 minutes (examples 5 to 19), heating at 140 ℃ for 10 minutes (examples 5 to 20), heating at 150 ℃ for 1 minute (examples 5 to 21), heating at 150 ℃ for 3 minutes (examples 5 to 22), heating at 150 ℃ for 5 minutes (examples 5 to 23), heating at 150 ℃ for 7.5 minutes (examples 3 to 24), heating at 150 ℃ for 10 minutes (examples 5 to 25), heating at 160 ℃ for 1 minute (examples 5 to 26), heating at 160 ℃ for 3 minutes (examples 5 to 27), heating at 160 ℃ for 5 minutes (examples 5 to 28), and heating at 160 ℃ for 7.5 minutes (examples 5 to 29), The same measurements and evaluations were carried out as in test example 5-1, except for the prebaking step of heating at 160 ℃ for 10 minutes (test examples 5-30), at 170 ℃ for 1 minute (test examples 5-31), at 170 ℃ for 3 minutes (test examples 5-32), at 170 ℃ for 5 minutes (test examples 5-33), at 180 ℃ for 1 minute (test examples 5-34), at 180 ℃ for 3 minutes (test examples 5-35), and at 190 ℃ for 1 minute (test examples 5-36). The results are shown below and in fig. 2C.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403 (test example 5-2 to test example 5-36)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 51745, molecular weight distribution: 1.400 (test 5-2)
Weight average molecular weight: 51745, molecular weight distribution: 1.400 (test examples 5-3)
Weight average molecular weight: 51284, molecular weight distribution: 1.402 (test examples 5-4)
Weight average molecular weight: 51745, molecular weight distribution: 1.400 (test examples 5-5)
Weight average molecular weight: 51685, molecular weight distribution: 1.400 (test examples 5 to 6)
Weight average molecular weight: 51082, molecular weight distribution: 1.409 (test examples 5 to 7)
Weight average molecular weight: 51284, molecular weight distribution: 1.402 (test examples 5-8)
Weight average molecular weight: 51745, molecular weight distribution: 1.400 (test examples 5 to 9)
Weight average molecular weight: 51685, molecular weight distribution: 1.400 (test examples 5 to 10)
Weight average molecular weight: 51007, molecular weight distribution: 1.403 (test examples 5 to 11)
Weight average molecular weight: 50817, molecular weight distribution: 1.404 (test examples 5-12)
Weight average molecular weight: 50554, molecular weight distribution: 1.404 (test examples 5-13)
Weight average molecular weight: 51036, molecular weight distribution: 1.406 (test examples 5 to 14)
Weight average molecular weight: 50824, molecular weight distribution: 1.402 (test examples 5 to 15)
Weight average molecular weight: 51007, molecular weight distribution: 1.403 (test examples 5 to 16)
Weight average molecular weight: 50024, molecular weight distribution: 1.400 (test examples 5 to 17)
Weight average molecular weight: 50696, molecular weight distribution: 1.404 (test examples 5-18)
Weight average molecular weight: 50620, molecular weight distribution: 1.407 (test examples 5 to 19)
Weight average molecular weight: 50513, molecular weight distribution: 1.410 (test examples 5-20)
Weight average molecular weight: 51007, molecular weight distribution: 1.403 (test examples 5 to 21)
Weight average molecular weight: 50817, molecular weight distribution: 1.401 (test examples 5 to 22)
Weight average molecular weight: 50859, molecular weight distribution: 1.412 (test examples 5 to 23)
Weight average molecular weight: 50841, molecular weight distribution: 1.436 (test examples 5 to 24)
Weight average molecular weight: 50611, molecular weight distribution: 1.432 (test examples 5 to 25)
Weight average molecular weight: 51007, molecular weight distribution: 1.403 (test examples 5 to 26)
Weight average molecular weight: 50582, molecular weight distribution: 1.413 (test examples 5-27)
Weight average molecular weight: 50418, molecular weight distribution: 1.414 (test examples 5 to 28)
Weight average molecular weight: 50437, molecular weight distribution: 1.417 (test examples 5 to 29)
Weight average molecular weight: 50408, molecular weight distribution: 1.416 (test examples 5-30)
Weight average molecular weight: 51007, molecular weight distribution: 1.403 (test examples 5 to 31)
Weight average molecular weight: 49672, molecular weight distribution: 1.418 (test examples 5 to 32)
Weight average molecular weight: 50334, molecular weight distribution: 1.415 (test examples 5 to 33)
Weight average molecular weight: 51007, molecular weight distribution: 1.403 (test examples 5 to 34)
Weight average molecular weight: 50150, molecular weight distribution: 1.417 (test examples 5 to 35)
Weight average molecular weight: 51007, molecular weight distribution: 1.403 (test examples 5 to 36)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 100.4%, retention rate evaluation result: a (good retention) (test example 5-2)
Retention ratio: 100.3%, retention rate evaluation result: a (good retention) (test examples 5 to 3)
Retention ratio: 99.5%, retention rate evaluation result: a (good retention) (test examples 5 to 4)
Retention ratio: 100.4%, retention rate evaluation result: a (good retention) (test examples 5 to 5)
Retention ratio: 100.3%, retention rate evaluation result: a (good retention) (test examples 5 to 6)
Retention ratio: 99.1%, retention rate evaluation result: a (good retention) (test examples 5 to 7)
Retention ratio: 99.5%, retention rate evaluation result: a (good retention) (test examples 5 to 8)
Retention ratio: 100.4%, retention rate evaluation result: a (good retention) (test examples 5 to 9)
Retention ratio: 100.3%, retention rate evaluation result: a (good retention) (test examples 5 to 10)
Retention ratio: 99.0%, retention rate evaluation result: a (good retention) (test examples 5 to 11)
Retention ratio: 98.6%, retention rate evaluation result: a (good retention) (test examples 5 to 12)
Retention ratio: 98.1%, retention rate evaluation result: a (good retention) (test examples 5 to 13)
Retention ratio: 99.1%, retention rate evaluation result: a (good retention) (test examples 5 to 14)
Retention ratio: 98.6%, retention rate evaluation result: a (good retention) (test examples 5 to 15)
Retention ratio: 99.0%, retention rate evaluation result: a (good retention) (test examples 5 to 16)
Retention ratio: 97.1%, retention rate evaluation result: a (good retention) (test examples 5 to 17)
Retention ratio: 98.4%, retention rate evaluation result: a (good retention) (test examples 5 to 18)
Retention ratio: 98.2%, retention rate evaluation result: a (good retention) (test examples 5 to 19)
Retention ratio: 98.0%, retention rate evaluation result: a (good retention) (test examples 5 to 20)
Retention ratio: 99.0%, retention rate evaluation result: a (good retention) (test examples 5 to 21)
Retention ratio: 98.6%, retention rate evaluation result: a (good retention) (test examples 5 to 22)
Retention ratio: 98.7%, retention rate evaluation result: a (good retention) (test examples 5 to 23)
Retention ratio: 98.7%, retention rate evaluation result: a (good retention) (test examples 5 to 24)
Retention ratio: 98.2%, retention rate evaluation result: a (good retention) (test examples 5 to 25)
Retention ratio: 99.0%, retention rate evaluation result: a (good retention) (test examples 5 to 26)
Retention ratio: 98.2%, retention rate evaluation result: a (good retention) (test examples 5 to 27)
Retention ratio: 97.9%, retention rate evaluation result: a (good retention) (test examples 5 to 28)
Retention ratio: 97.9%, retention rate evaluation result: a (good retention) (test examples 5 to 29)
Retention ratio: 97.8%, retention rate evaluation result: a (good retention) (test examples 5 to 30)
Retention ratio: 99.0%, retention rate evaluation result: a (good retention) (test examples 5 to 31)
Retention ratio: 96.4%, retention rate evaluation result: a (good retention) (test examples 5 to 32)
Retention ratio: 97.7%, retention rate evaluation result: a (good retention) (test examples 5 to 33)
Retention ratio: 99.0%, retention rate evaluation result: a (good retention) (test examples 5 to 34)
Retention ratio: 97.3%, retention rate evaluation result: a (good retention) (test examples 5 to 35)
Retention ratio: 99.0%, retention rate evaluation result: a (good retention) (test examples 5 to 36)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good adhesion) (test examples 5-2 to 5-36)
(test examples 5-37 to 5-40)
"preparation of Polymer (F5)," preparation of Positive resist composition, "and" formation of resist Pattern "were carried out in the same manner as in test example 5-1 except that the prebaking step was carried out for heating at 90 ℃ for 7.5 minutes (test examples 5-37), heating at 100 ℃ for 5 minutes (test examples 5-38), heating at 110 ℃ for 3 minutes (test examples 5-39), and heating at 120 ℃ for 1 minute (test examples 5-40), respectively, instead of the prebaking step carried out for heating at 90 ℃ for 10 minutes in test example 5-1. The results are shown below and in fig. 2C.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403 (test examples 5-37 to 5-40)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 51745, molecular weight distribution: 1.400 (test examples 5-37)
Weight average molecular weight: 51284, molecular weight distribution: 1.402 (test examples 5-38)
Weight average molecular weight: 51082, molecular weight distribution: 1.409 (test examples 5-39)
Weight average molecular weight: 51007, molecular weight distribution: 1.403 (test examples 5-40)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 100.4%, retention rate evaluation result: a (good retention) (test examples 5 to 37)
Retention ratio: 99.5%, retention rate evaluation result: a (good retention) (test examples 5 to 38)
Retention ratio: 99.1%, retention rate evaluation result: a (good retention) (test examples 5 to 39)
Retention ratio: 99.0%, retention rate evaluation result: a (good retention) (test examples 5 to 40)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: b (Low adhesion) (test examples 5-37 to 5-40)
(test examples 5-41 to 5-44)
"preparation of Polymer (F5)," preparation of Positive resist composition, "and" formation of resist Pattern "were carried out in the same manner as in test example 5-1 except that the prebaking step was carried out at 170 ℃ for 7.5 minutes (test examples 5-41), at 170 ℃ for 10 minutes (test examples 5-42), at 180 ℃ for 5 minutes (test examples 5-43), and at 190 ℃ for 3 minutes (test examples 5-44), instead of the prebaking step at 90 ℃ for 10 minutes carried out in test example 5-1, respectively, and the same measurements and evaluations were carried out. The results are shown below and in fig. 2C.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403 (test examples 5-41 to 5-44)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 49012, molecular weight distribution: 1.441 (test examples 5-41)
Weight average molecular weight: 48023, molecular weight distribution: 1.454 (test examples 5 to 42)
Weight average molecular weight: 48121, molecular weight distribution: 1.435 (test examples 5-43)
Weight average molecular weight: 48307, molecular weight distribution: 1.437 (test examples 5-44)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 95.1%, retention rate evaluation result: b (retention ratio is small) (test examples 5 to 41)
Retention ratio: 93.2%, retention rate evaluation result: b (maintenance ratio is small) (test examples 5 to 42)
Retention ratio: 93.4%, retention rate evaluation result: b (maintenance ratio is small) (test examples 5 to 43)
Retention ratio: 93.8%, retention rate evaluation result: b (maintenance ratio is small) (test examples 5 to 44)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good adhesion) (test examples 5-41 to 5-44)
Example 6
(test example 6-1)
"preparation of Polymer (F6)," preparation of Positive resist composition, "and" formation of resist Pattern "were carried out in the same manner as in test example 2-1 except that isobutyl formate was used instead of isoamyl acetate used in test example 2-1 and that a prebaking step was carried out at 90 ℃ for 10 minutes instead of the prebaking step at 120 ℃ for 10 minutes. The results are shown in text and in FIG. 3C.
< measurement evaluation results >
The evaluation results of the measured weight average molecular weight and molecular weight distribution, weight average molecular weight retention ratio, and adhesion are shown below and in fig. 3C.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 48980, molecular weight distribution: 1.283
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 103.5%, retention rate evaluation result: a (good and high retention)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing)
(test examples 6-2 to 6-44)
Instead of the prebaking step of heating at 90 ℃ for 10 minutes as in test example 6-1, heating at 100 ℃ for 7.5 minutes (test example 6-2), heating at 100 ℃ for 10 minutes (test example 6-3), heating at 110 ℃ for 5 minutes (test example 6-4), heating at 110 ℃ for 7.5 minutes (test example 6-5), heating at 110 ℃ for 10 minutes (test example 6-6), heating at 120 ℃ for 3 minutes (test example 6-7), heating at 120 ℃ for 5 minutes (test example 6-8), heating at 120 ℃ for 7.5 minutes (test example 6-9), heating at 120 ℃ for 10 minutes (test example 6-10), heating at 130 ℃ for 1 minute (test example 6-11), heating at 130 ℃ for 3 minutes (test example 6-12), heating at 130 ℃ for 5 minutes (test example 6-13), and heating at 130 ℃ for 7.5 minutes (test example 6-14) were carried out, Heating at 130 ℃ for 10 minutes (examples 6 to 15), heating at 140 ℃ for 1 minute (examples 6 to 16), heating at 140 ℃ for 3 minutes (examples 6 to 17), heating at 140 ℃ for 5 minutes (examples 6 to 18), heating at 140 ℃ for 7.5 minutes (examples 6 to 19), heating at 140 ℃ for 10 minutes (examples 6 to 20), heating at 150 ℃ for 1 minute (examples 6 to 21), heating at 150 ℃ for 3 minutes (examples 6 to 22), heating at 150 ℃ for 5 minutes (examples 6 to 23), heating at 150 ℃ for 7.5 minutes (examples 6 to 24), heating at 150 ℃ for 10 minutes (examples 6 to 25), heating at 160 ℃ for 1 minute (examples 6 to 26), heating at 160 ℃ for 3 minutes (examples 6 to 27), heating at 160 ℃ for 5 minutes (examples 6 to 28), and heating at 160 ℃ for 7.5 minutes (examples 6 to 29), A pre-baking step of heating at 160 ℃ for 10 minutes (test examples 6 to 30), at 170 ℃ for 1 minute (test examples 6 to 31), at 170 ℃ for 3 minutes (test examples 6 to 32), at 170 ℃ for 5 minutes (test examples 6 to 33), at 170 ℃ for 7.5 minutes (test examples 6 to 34), at 170 ℃ for 10 minutes (test examples 6 to 35), at 180 ℃ for 1 minute (test examples 6 to 36), at 180 ℃ for 3 minutes (test examples 6 to 37), at 180 ℃ for 5 minutes (test examples 6 to 38), at 180 ℃ for 7.5 minutes (test examples 6 to 39), at 180 ℃ for 10 minutes (test examples 6 to 40), at 190 ℃ for 1 minute (test examples 6 to 41), at 190 ℃ for 3 minutes (test examples 6 to 42), at 190 ℃ for 5 minutes (test examples 6 to 43), and at 190 ℃ for 7.5 minutes (test examples 6 to 44), except for this, the same measurements and evaluations as in test example 6-1 were carried out for "production of polymer (F6)", "production of positive resist composition", and "formation of resist pattern". The results are shown below and in fig. 3C.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284 (test example 6-2 to 6-44)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 49001 molecular weight distribution: 1.283 (test example 6-2)
Weight average molecular weight: 48980, molecular weight distribution: 1.283 (test example 6-3)
Weight average molecular weight: 49055, molecular weight distribution: 1.286 (test examples 6-4)
Weight average molecular weight: 49001 molecular weight distribution: 1.283 (test example 6-5)
Weight average molecular weight: 48980, molecular weight distribution: 1.283 (test example 6-6)
Weight average molecular weight: 48999, molecular weight distribution: 1.288 (test examples 6-7)
Weight average molecular weight: 49055, molecular weight distribution: 1.286 (test examples 6 to 8)
Weight average molecular weight: 49001 molecular weight distribution: 1.283 (test examples 6-9)
Weight average molecular weight: 48980, molecular weight distribution: 1.283 (test examples 6-10)
Weight average molecular weight: 47547, molecular weight distribution: 1.289 (test examples 6 to 11)
Weight average molecular weight: 48195, molecular weight distribution: 1.276 (test examples 6-12)
Weight average molecular weight: 49074 molecular weight distribution: 1.285 (test examples 6-13)
Weight average molecular weight: 49001 molecular weight distribution: 1.282 (test examples 6 to 14)
Weight average molecular weight: 48552, molecular weight distribution: 1.284 (test examples 6 to 15)
Weight average molecular weight: 47547, molecular weight distribution: 1.285 (test examples 6-16)
Weight average molecular weight: 48438, molecular weight distribution: 1.283 (test examples 6-17)
Weight average molecular weight: 48091, molecular weight distribution: 1.285 (test examples 6-18)
Weight average molecular weight: 47829, molecular weight distribution: 1.284 (test examples 6 to 19)
Weight average molecular weight: 47664, molecular weight distribution: 1.285 (test examples 6-20)
Weight average molecular weight: 48254, molecular weight distribution: 1.288 (test examples 6 to 21)
Weight average molecular weight: 48710, molecular weight distribution: 1.285 (test examples 6-22)
Weight average molecular weight: 48174, molecular weight distribution: 1.288 (test examples 6-23)
Weight average molecular weight: 48312, molecular weight distribution: 1.291 (test examples 6-24)
Weight average molecular weight: 48317, molecular weight distribution: 1.289 (test examples 6 to 25)
Weight average molecular weight: 48018, molecular weight distribution: 1.282 (test examples 6 to 26)
Weight average molecular weight: 48294, molecular weight distribution: 1.288 (test examples 6 to 27)
Weight average molecular weight: 47739, molecular weight distribution: 1.292 (test examples 6 to 28)
Weight average molecular weight: 47543, molecular weight distribution: 1.300 (test examples 6 to 29)
Weight average molecular weight: 47127, molecular weight distribution: 1.299 (test examples 6 to 30)
Weight average molecular weight: 47174, molecular weight distribution: 1.284 (test examples 6 to 31)
Weight average molecular weight: 48079, molecular weight distribution: 1.293 (test examples 6-32)
Weight average molecular weight: 47218, molecular weight distribution: 1.302 (test examples 6-33)
Weight average molecular weight: 46972, molecular weight distribution: 1.313 (test examples 6-34)
Weight average molecular weight: 46546, molecular weight distribution: 1.310 (test examples 6 to 35)
Weight average molecular weight: 48008, molecular weight distribution: 1.291 (test examples 6-36)
Weight average molecular weight: 47597, molecular weight distribution: 1.301 (test examples 6-37)
Weight average molecular weight: 46227, molecular weight distribution: 1.318 (test examples 6 to 38)
Weight average molecular weight: 46231, molecular weight distribution: 1.317 (test examples 6-39)
Weight average molecular weight: 46266, molecular weight distribution: 1.322 (test example 6-40)
Weight average molecular weight: 47934, molecular weight distribution: 1.299 (test examples 6-41)
Weight average molecular weight: 47165, molecular weight distribution: 1.306 (test examples 6 to 42)
Weight average molecular weight: 45937, molecular weight distribution: 1.318 (test examples 6 to 43)
Weight average molecular weight: 45743, molecular weight distribution: 1.329 (test examples 6-44)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 103.6%, retention rate evaluation result: a (good retention ratio) (test example 6-2)
Retention ratio: 103.5%, retention rate evaluation result: a (good retention) (test examples 6-3)
Retention ratio: 103.7%, retention rate evaluation result: a (good retention) (test examples 6-4)
Retention ratio: 103.6%, retention rate evaluation result: a (good retention) (test examples 6-5)
Retention ratio: 103.5%, retention rate evaluation result: a (good retention) (test examples 6-6)
Retention ratio: 103.6%, retention rate evaluation result: a (good retention) (test examples 6 to 7)
Retention ratio: 103.7%, retention rate evaluation result: a (good retention) (test examples 6 to 8)
Retention ratio: 103.6%, retention rate evaluation result: a (good retention) (test examples 6 to 9)
Retention ratio: 103.5%, retention rate evaluation result: a (good retention) (test examples 6-10)
Retention ratio: 100.5%, retention rate evaluation result: a (good retention) (test examples 6 to 11)
Retention ratio: 101.9%, retention rate evaluation result: a (good retention) (test examples 6 to 12)
Retention ratio: 103.7%, retention rate evaluation result: a (good retention) (test examples 6 to 13)
Retention ratio: 103.6%, retention rate evaluation result: a (good retention) (test examples 6 to 14)
Retention ratio: 102.6%, retention rate evaluation result: a (good retention) (test examples 6 to 15)
Retention ratio: 100.5%, retention rate evaluation result: a (good retention) (test examples 6 to 16)
Retention ratio: 102.4%, retention rate evaluation result: a (good retention) (test examples 6 to 17)
Retention ratio: 101.6%, retention rate evaluation result: a (good retention) (test examples 6 to 18)
Retention ratio: 101.1%, retention rate evaluation result: a (good retention) (test examples 6 to 19)
Retention ratio: 100.7%, retention rate evaluation result: a (good retention ratio) (test examples 6 to 20)
Retention ratio: 102.0%, retention rate evaluation result: a (good retention) (test examples 6 to 21)
Retention ratio: 103.0%, retention rate evaluation result: a (good retention) (test examples 6 to 22)
Retention ratio: 101.8%, retention rate evaluation result: a (good retention) (test examples 6 to 23)
Retention ratio: 102.1%, retention rate evaluation result: a (good retention) (test examples 6 to 24)
Retention ratio: 102.1%, retention rate evaluation result: a (good retention) (test examples 6 to 25)
Retention ratio: 101.5%, retention rate evaluation result: a (good retention) (test examples 6 to 26)
Retention ratio: 102.1%, retention rate evaluation result: a (good retention) (test examples 6 to 27)
Retention ratio: 100.9%, retention rate evaluation result: a (good retention) (test examples 6 to 28)
Retention ratio: 100.5%, retention rate evaluation result: a (good retention) (test examples 6 to 29)
Retention ratio: 99.6%, retention rate evaluation result: a (good retention) (test examples 6 to 30)
Retention ratio: 99.7%, retention rate evaluation result: a (good retention) (test examples 6 to 31)
Retention ratio: 101.6%, retention rate evaluation result: a (good retention) (test examples 6 to 32)
Retention ratio: 99.8%, retention rate evaluation result: a (good retention) (test examples 6 to 33)
Retention ratio: 99.3%, retention rate evaluation result: a (good retention) (test examples 6 to 34)
Retention ratio: 98.4%, retention rate evaluation result: a (good retention) (test examples 6 to 35)
Retention ratio: 101.5%, retention rate evaluation result: a (good retention) (test examples 6 to 36)
Retention ratio: 100.6%, retention rate evaluation result: a (good retention) (test examples 6 to 37)
Retention ratio: 97.7%, retention rate evaluation result: a (good retention) (test examples 6 to 38)
Retention ratio: 97.7%, retention rate evaluation result: a (good retention) (test examples 6-39)
Retention ratio: 97.8%, retention rate evaluation result: a (good retention) (test examples 6-40)
Retention ratio: 101.3%, retention rate evaluation result: a (good retention) (test examples 6-41)
Retention ratio: 99.7%, retention rate evaluation result: a (good retention) (test examples 6 to 42)
Retention ratio: 97.1%, retention rate evaluation result: a (good retention) (test examples 6 to 43)
Retention ratio: 96.7%, retention rate evaluation result: a (good retention) (test examples 6 to 44)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing property) (test examples 6-2 to 6-44)
(test examples 6-45 to 6-48)
"preparation of Polymer (F6)," preparation of Positive resist composition, "and" formation of resist Pattern "were carried out in the same manner as in test example 6-1 except that the prebaking step was carried out for heating at 90 ℃ for 7.5 minutes (test examples 6-45), heating at 100 ℃ for 5 minutes (test examples 6-46), heating at 110 ℃ for 3 minutes (test examples 6-47), and heating at 120 ℃ for 1 minute (test examples 6-48), respectively, instead of the prebaking step carried out for heating at 90 ℃ for 10 minutes in test example 6-1. The results are shown below and in fig. 3C.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284 (test examples 6-45 to 6-48)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 49001 molecular weight distribution: 1.283 (test examples 6-45)
Weight average molecular weight: 49055, molecular weight distribution: 1.286 (test examples 6 to 46)
Weight average molecular weight: 48999, molecular weight distribution: 1.288 (test examples 6-47)
Weight average molecular weight: 47314, molecular weight distribution: 1.285 (test examples 6-48)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 103.6%, retention rate evaluation result: a (good retention) (test examples 6 to 45)
Retention ratio: 103.7%, retention rate evaluation result: a (good retention) (test examples 6 to 46)
Retention ratio: 103.6%, retention rate evaluation result: a (good retention ratio) (test examples 6 to 47)
Retention ratio: 100.0%, retention rate evaluation result: a (good retention) (test examples 6 to 48)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: b (Low adhesion) (test examples 6-45 to 6-48)
(test examples 6 to 49)
"preparation of Polymer (F6)," preparation of Positive resist composition, "and" formation of resist Pattern "were carried out in the same manner as in test example 6-1 except that the prebaking step of heating at 90 ℃ for 10 minutes and the prebaking step of heating at 190 ℃ for 10 minutes were carried out in place of the prebaking step of heating at 90 ℃ for 10 minutes carried out in test example 6-1, and the same measurements and evaluations were carried out. The results are shown below and in fig. 3C.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 44504, molecular weight distribution: 1.347
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 94.1%, retention rate evaluation result: b (retention rate is small)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing)
Example 7
(test example 7-1)
"preparation of Polymer (F5)," preparation of Positive resist composition, "and" formation of resist Pattern "were carried out in the same manner as in test example 1-1 except that n-pentyl formate was used instead of isoamyl acetate used in test example 1-1 and that a prebaking step was carried out at 110 ℃ for 10 minutes instead of the prebaking step at 120 ℃ for 10 minutes. The results are shown below and in fig. 2D.
< measurement evaluation results >
The measured weight average molecular weight and molecular weight distribution, the evaluation results of the weight average molecular weight retention rate, and the evaluation results of the adhesion are shown below and in fig. 2D.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 51690, molecular weight distribution: 1.400
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 100.3%, retention rate evaluation result: a (good and high retention)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing)
(test examples 7-2 to 7-26)
Instead of the prebaking step of heating at 110 ℃ for 10 minutes as in test example 7-1, heating at 120 ℃ for 7.5 minutes (test example 7-2), heating at 120 ℃ for 10 minutes (test example 7-3), heating at 130 ℃ for 5 minutes (test example 7-4), heating at 130 ℃ for 7.5 minutes (test example 7-5), heating at 130 ℃ for 10 minutes (test example 7-6), heating at 140 ℃ for 3 minutes (test example 7-7), heating at 140 ℃ for 5 minutes (test example 7-8), heating at 140 ℃ for 7.5 minutes (test example 7-9), heating at 140 ℃ for 10 minutes (test example 7-10), heating at 150 ℃ for 1 minute (test example 7-11), heating at 150 ℃ for 3 minutes (test example 7-12), heating at 150 ℃ for 5 minutes (test example 7-13), heating at 150 ℃ for 7.5 minutes (test example 7-14) were carried out, The prebaking process of "preparation of Polymer (F5)", "preparation of Positive resist composition" ("preparation of Positive resist composition") was carried out in the same manner as in test example 7-1 except for the steps of heating at 150 ℃ for 10 minutes (test examples 7-15), heating at 160 ℃ for 1 minute (test examples 7-16), heating at 160 ℃ for 3 minutes (test examples 7-17), heating at 160 ℃ for 5 minutes (test examples 7-18), heating at 160 ℃ for 7.5 minutes (test examples 7-19), heating at 160 ℃ for 10 minutes (test examples 7-20), heating at 170 ℃ for 1 minute (test examples 7-21), heating at 170 ℃ for 3 minutes (test examples 7-22), heating at 170 ℃ for 5 minutes (test examples 7-23), heating at 180 ℃ for 1 minute (test examples 7-24), heating at 180 ℃ for 3 minutes (test examples 7-25), and heating at 190 ℃ for 1 minute (test examples 7-26), "formation of resist pattern" was measured and evaluated in the same manner. The results are shown below and in fig. 2D.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403 (test examples 7-2 to 7-26)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 51808, molecular weight distribution: 1.400 (test 7-2)
Weight average molecular weight: 51690, molecular weight distribution: 1.400 (test 7-3)
Weight average molecular weight: 50620, molecular weight distribution: 1.404 (test examples 7-4)
Weight average molecular weight: 51098, molecular weight distribution: 1.406 (test examples 7 to 5)
Weight average molecular weight: 50829, molecular weight distribution: 1.402 (test examples 7-6)
Weight average molecular weight: 50014, molecular weight distribution: 1.400 (test examples 7-7)
Weight average molecular weight: 50762, molecular weight distribution: 1.404 (test examples 7-8)
Weight average molecular weight: 50681, molecular weight distribution: 1.407 (test examples 7 to 9)
Weight average molecular weight: 50518, molecular weight distribution: 1.410 (test examples 7 to 10)
Weight average molecular weight: 51429, molecular weight distribution: 1.403 (test examples 7 to 11)
Weight average molecular weight: 50806, molecular weight distribution: 1.401 (test examples 7 to 12)
Weight average molecular weight: 50926, molecular weight distribution: 1.412 (test examples 7 to 13)
Weight average molecular weight: 50902, molecular weight distribution: 1.436 (test examples 7 to 14)
Weight average molecular weight: 50616, molecular weight distribution: 1.432 (test examples 7-15)
Weight average molecular weight: 51429, molecular weight distribution: 1.403 (test examples 7-16)
Weight average molecular weight: 50572, molecular weight distribution: 1.413 (test examples 7-17)
Weight average molecular weight: 50484, molecular weight distribution: 1.414 (test examples 7-18)
Weight average molecular weight: 50498, molecular weight distribution: 1.417 (test examples 7-19)
Weight average molecular weight: 50414, molecular weight distribution: 1.416 (test examples 7-20)
Weight average molecular weight: 51429, molecular weight distribution: 1.403 (test examples 7 to 21)
Weight average molecular weight: 49662, molecular weight distribution: 1.418 (test examples 7 to 22)
Weight average molecular weight: 50400, molecular weight distribution: 1.415 (test examples 7-23)
Weight average molecular weight: 51429, molecular weight distribution: 1.403 (test examples 7 to 24)
Weight average molecular weight: 50140, molecular weight distribution: 1.417 (test examples 7-25)
Weight average molecular weight: 51429, molecular weight distribution: 1.403 (test examples 7 to 26)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 100.6%, retention rate evaluation result: a (good retention ratio) (test example 7-2)
Retention ratio: 100.3%, retention rate evaluation result: a (good retention) (test examples 7-3)
Retention ratio: 98.2%, retention rate evaluation result: a (good retention) (test examples 7-4)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 7-5)
Retention ratio: 98.7%, retention rate evaluation result: a (good retention) (test examples 7-6)
Retention ratio: 97.1%, retention rate evaluation result: a (good retention) (test examples 7 to 7)
Retention ratio: 98.5%, retention rate evaluation result: a (good retention) (test examples 7 to 8)
Retention ratio: 98.4%, retention rate evaluation result: a (good retention) (test examples 7 to 9)
Retention ratio: 98.1%, retention rate evaluation result: a (good retention) (test examples 7 to 10)
Retention ratio: 99.8%, retention rate evaluation result: a (good retention) (test examples 7 to 11)
Retention ratio: 98.6%, retention rate evaluation result: a (good retention) (test examples 7 to 12)
Retention ratio: 98.8%, retention rate evaluation result: a (good retention) (test examples 7 to 13)
Retention ratio: 98.8%, retention rate evaluation result: a (good retention) (test examples 7 to 14)
Retention ratio: 98.2%, retention rate evaluation result: a (good retention) (test examples 7 to 15)
Retention ratio: 99.8%, retention rate evaluation result: a (good retention) (test examples 7 to 16)
Retention ratio: 98.2%, retention rate evaluation result: a (good retention) (test examples 7 to 17)
Retention ratio: 98.0%, retention rate evaluation result: a (good retention) (test examples 7 to 18)
Retention ratio: 98.0%, retention rate evaluation result: a (good retention) (test examples 7 to 19)
Retention ratio: 97.8%, retention rate evaluation result: a (good retention) (test examples 7-20)
Retention ratio: 99.8%, retention rate evaluation result: a (good retention) (test examples 7 to 21)
Retention ratio: 96.4%, retention rate evaluation result: a (good retention) (test examples 7 to 22)
Retention ratio: 97.8%, retention rate evaluation result: a (good retention) (test examples 7 to 23)
Retention ratio: 99.8%, retention rate evaluation result: a (good retention) (test examples 7 to 24)
Retention ratio: 97.3%, retention rate evaluation result: a (good retention) (test examples 7 to 25)
Retention ratio: 99.8%, retention rate evaluation result: a (good retention) (test examples 7 to 26)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing property) (test examples 7-2 to 7-26)
(test examples 7-27 to 7-31)
The same measurements and evaluations as in test example 7-1 were carried out for "preparation of polymer (F5)", "preparation of positive resist composition", and "formation of resist pattern", except that the prebaking step was carried out for heating at 100 ℃ for 10 minutes (test examples 7 to 27), at 110 ℃ for 7.5 minutes (test examples 7 to 28), at 120 ℃ for 5 minutes (test examples 7 to 29), at 130 ℃ for 3 minutes (test examples 7 to 30), and at 140 ℃ for 1 minute (test examples 7 to 31), respectively, instead of the prebaking step carried out for heating at 110 ℃ for 10 minutes in test example 7-1. The results are shown below and in fig. 2D.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403 (test examples 7-27 to 7-31)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 51690, molecular weight distribution: 1.400 (test examples 7 to 27)
Weight average molecular weight: 51808, molecular weight distribution: 1.400 (test examples 7 to 28)
Weight average molecular weight: 51352, molecular weight distribution: 1.402 (test examples 7 to 29)
Weight average molecular weight: 50806, molecular weight distribution: 1.404 (test examples 7-30)
Weight average molecular weight: 51429, molecular weight distribution: 1.403 (test examples 7-31)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 100.3%, retention rate evaluation result: a (good retention) (test examples 7 to 27)
Retention ratio: 100.6%, retention rate evaluation result: a (good retention) (test examples 7 to 28)
Retention ratio: 99.7%, retention rate evaluation result: a (good retention) (test examples 7 to 29)
Retention ratio: 98.6%, retention rate evaluation result: a (good retention) (test examples 7 to 30)
Retention ratio: 99.8%, retention rate evaluation result: a (good retention) (test examples 7 to 31)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: b (Low adhesion) (test examples 7-27 to 7-31)
(test examples 7-32 to 7-35)
"preparation of Polymer (F5)," preparation of Positive resist composition, "and" formation of resist Pattern "were carried out in the same manner as in test example 7-1 except that the prebaking step was carried out for heating at 170 ℃ for 7.5 minutes (test examples 7-32), at 170 ℃ for 10 minutes (test examples 7-33), at 180 ℃ for 5 minutes (test examples 7-34), and at 190 ℃ for 3 minutes (test examples 7-35), instead of the prebaking step at 110 ℃ for 10 minutes which was carried out in test example 7-1, and the same measurements and evaluations were carried out. The results are shown below and in fig. 2D.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403 (test examples 7-32 to 7-35)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 49206, molecular weight distribution: 1.437 (test examples 7-32)
Weight average molecular weight: 48735, molecular weight distribution: 1.452 (test examples 7-33)
Weight average molecular weight: 47836, molecular weight distribution: 1.448 (test examples 7-34)
Weight average molecular weight: 48297, molecular weight distribution: 1.437 (test examples 7-35)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 95.5%, retention rate evaluation result: b (maintenance ratio is small) (test examples 7 to 32)
Retention ratio: 94.6%, retention rate evaluation result: b (maintenance ratio is small) (test examples 7 to 33)
Retention ratio: 92.8%, retention rate evaluation result: b (maintenance ratio is small) (test examples 7 to 34)
Retention ratio: 93.7%, retention rate evaluation result: b (maintenance ratio is small) (test examples 7 to 35)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing property) (test examples 7-32 to 7-35)
Example 8
(test example 8-1)
"preparation of Polymer (F6)," preparation of Positive resist composition, "and" formation of resist Pattern "were carried out in the same manner as in test example 2-1 except that n-pentyl formate was used instead of isoamyl acetate used in test example 2-1 and that a prebaking step was carried out at 110 ℃ for 10 minutes instead of the prebaking step at 120 ℃ for 10 minutes. The results are shown below and in fig. 3D.
< measurement evaluation results >
The results of evaluation of the measured weight average molecular weight and molecular weight distribution, weight average molecular weight retention rate, and adhesion are shown below and in fig. 3D.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 48614, molecular weight distribution: 1.283
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 102.8%, retention rate evaluation result: a (good and high retention)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing)
(test examples 8-2 to 8-34)
Instead of the prebaking step of heating at 110 ℃ for 10 minutes as in test example 8-1, heating at 120 ℃ for 7.5 minutes (test example 8-2), heating at 120 ℃ for 10 minutes (test example 8-3), heating at 130 ℃ for 5 minutes (test example 8-4), heating at 130 ℃ for 7.5 minutes (test example 8-5), heating at 130 ℃ for 10 minutes (test example 8-6), heating at 140 ℃ for 3 minutes (test example 8-7), heating at 140 ℃ for 5 minutes (test example 8-8), heating at 140 ℃ for 7.5 minutes (test example 8-9), heating at 140 ℃ for 10 minutes (test example 8-10), heating at 150 ℃ for 1 minute (test example 8-11), heating at 150 ℃ for 3 minutes (test example 8-12), heating at 150 ℃ for 5 minutes (test example 8-13), heating at 150 ℃ for 7.5 minutes (test example 8-14) were carried out, Heating at 150 ℃ for 10 minutes (examples 8 to 15), heating at 160 ℃ for 1 minute (examples 8 to 16), heating at 160 ℃ for 3 minutes (examples 8 to 17), heating at 160 ℃ for 5 minutes (examples 8 to 18), heating at 160 ℃ for 7.5 minutes (examples 8 to 19), heating at 160 ℃ for 10 minutes (examples 8 to 20), heating at 170 ℃ for 1 minute (examples 8 to 21), heating at 170 ℃ for 3 minutes (examples 8 to 22), heating at 170 ℃ for 5 minutes (examples 8 to 23), heating at 170 ℃ for 7.5 minutes (examples 8 to 24), heating at 170 ℃ for 10 minutes (examples 8 to 25), heating at 180 ℃ for 1 minute (examples 8 to 26), heating at 180 ℃ for 3 minutes (examples 8 to 27), heating at 180 ℃ for 5 minutes (examples 8 to 28), and heating at 180 ℃ for 7.5 minutes (examples 8 to 29), The same measurements and evaluations were carried out as in test example 8-1, except for the prebaking step of heating at 180 ℃ for 10 minutes (test examples 8-30), heating at 190 ℃ for 1 minute (test examples 8-31), heating at 190 ℃ for 3 minutes (test examples 8-32), heating at 190 ℃ for 5 minutes (test examples 8-33), and heating at 190 ℃ for 7.5 minutes (test examples 8-34). The results are shown below and in fig. 3D.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284 (test example 8-2 to 8-34)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 48775, molecular weight distribution: 1.286 (test example 8-2)
Weight average molecular weight: 48614, molecular weight distribution: 1.283 (test 8-3)
Weight average molecular weight: 47824, molecular weight distribution: 1.285 (test 8-4)
Weight average molecular weight: 48794, molecular weight distribution: 1.285 (test 8-5)
Weight average molecular weight: 48614, molecular weight distribution: 1.284 (test examples 8-6)
Weight average molecular weight: 47171, molecular weight distribution: 1.283 (test examples 8-7)
Weight average molecular weight: 48065, molecular weight distribution: 1.285 (test examples 8-8)
Weight average molecular weight: 47817, molecular weight distribution: 1.285 (test examples 8-9)
Weight average molecular weight: 47451, molecular weight distribution: 1.285 (test examples 8-10)
Weight average molecular weight: 47226, molecular weight distribution: 1.288 (test examples 8-11)
Weight average molecular weight: 47873, molecular weight distribution: 1.285 (test examples 8-12)
Weight average molecular weight: 48335, molecular weight distribution: 1.288 (test examples 8-13)
Weight average molecular weight: 47899, molecular weight distribution: 1.288 (test examples 8-14)
Weight average molecular weight: 47930, molecular weight distribution: 1.289 (test examples 8-15)
Weight average molecular weight: 47226, molecular weight distribution: 1.282 (test examples 8 to 16)
Weight average molecular weight: 47639, molecular weight distribution: 1.288 (test examples 8-17)
Weight average molecular weight: 47922, molecular weight distribution: 1.292 (test examples 8 to 18)
Weight average molecular weight: 47467, molecular weight distribution: 1.292 (test examples 8 to 19)
Weight average molecular weight: 47167, molecular weight distribution: 1.299 (test examples 8-20)
Weight average molecular weight: 47226, molecular weight distribution: 1.284 (test examples 8 to 21)
Weight average molecular weight: 46801, molecular weight distribution: 1.293 (test examples 8-22)
Weight average molecular weight: 47709, molecular weight distribution: 1.302 (test examples 8-23)
Weight average molecular weight: 46949, molecular weight distribution: 1.302 (test examples 8-24)
Weight average molecular weight: 46601, molecular weight distribution: 1.310 (test examples 8-25)
Weight average molecular weight: 47226, molecular weight distribution: 1.291 (test examples 8-26)
Weight average molecular weight: 47629, molecular weight distribution: 1.301 (test examples 8-27)
Weight average molecular weight: 47231, molecular weight distribution: 1.318 (test examples 8 to 28)
Weight average molecular weight: 45964, molecular weight distribution: 1.318 (test examples 8 to 29)
Weight average molecular weight: 45866, molecular weight distribution: 1.314 (test examples 8 to 30)
Weight average molecular weight: 47226, molecular weight distribution: 1.299 (test examples 8-31)
Weight average molecular weight: 47555, molecular weight distribution: 1.306 (test examples 8 to 32)
Weight average molecular weight: 46802, molecular weight distribution: 1.318 (test examples 8 to 33)
Weight average molecular weight: 45675, molecular weight distribution: 1.318 (test examples 8 to 34)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 103.1%, retention rate evaluation result: a (good retention ratio) (test example 8-2)
Retention ratio: 102.8%, retention rate evaluation result: a (good retention) (test examples 8-3)
Retention ratio: 101.1%, retention rate evaluation result: a (good retention) (test examples 8-4)
Retention ratio: 103.1%, retention rate evaluation result: a (good retention) (test examples 8 to 5)
Retention ratio: 102.8%, retention rate evaluation result: a (good retention) (test examples 8 to 6)
Retention ratio: 99.7%, retention rate evaluation result: a (good retention) (test examples 8 to 7)
Retention ratio: 101.6%, retention rate evaluation result: a (good retention) (test examples 8 to 8)
Retention ratio: 101.1%, retention rate evaluation result: a (good retention) (test examples 8 to 9)
Retention ratio: 100.3%, retention rate evaluation result: a (good retention) (test examples 8 to 10)
Retention ratio: 99.8%, retention rate evaluation result: a (good retention) (test examples 8 to 11)
Retention ratio: 101.2%, retention rate evaluation result: a (good retention) (test examples 8 to 12)
Retention ratio: 102.2%, retention rate evaluation result: a (good retention) (test examples 8 to 13)
Retention ratio: 101.2%, retention rate evaluation result: a (good retention) (test examples 8 to 14)
Retention ratio: 101.3%, retention rate evaluation result: a (good retention) (test examples 8 to 15)
Retention ratio: 99.8%, retention rate evaluation result: a (good retention) (test examples 8 to 16)
Retention ratio: 100.7%, retention rate evaluation result: a (good retention) (test examples 8 to 17)
Retention ratio: 101.3%, retention rate evaluation result: a (good retention) (test examples 8 to 18)
Retention ratio: 100.3%, retention rate evaluation result: a (good retention) (test examples 8 to 19)
Retention ratio: 99.7%, retention rate evaluation result: a (good retention ratio) (test examples 8 to 20)
Retention ratio: 99.8%, retention rate evaluation result: a (good retention) (test examples 8 to 21)
Retention ratio: 98.9%, retention rate evaluation result: a (good retention) (test examples 8 to 22)
Retention ratio: 100.8%, retention rate evaluation result: a (good retention) (test examples 8 to 23)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 8 to 24)
Retention ratio: 98.5%, retention rate evaluation result: a (good retention) (test examples 8 to 25)
Retention ratio: 99.8%, retention rate evaluation result: a (good retention) (test examples 8 to 26)
Retention ratio: 100.7%, retention rate evaluation result: a (good retention) (test examples 8 to 27)
Retention ratio: 99.8%, retention rate evaluation result: a (good retention) (test examples 8 to 28)
Retention ratio: 97.2%, retention rate evaluation result: a (good retention) (test examples 8 to 29)
Retention ratio: 96.9%, retention rate evaluation result: a (good retention) (test examples 8 to 30)
Retention ratio: 99.8%, retention rate evaluation result: a (good retention) (test examples 8 to 31)
Retention ratio: 100.5%, retention rate evaluation result: a (good retention) (test examples 8 to 32)
Retention ratio: 98.9%, retention rate evaluation result: a (good retention) (test examples 8 to 33)
Retention ratio: 96.5%, retention rate evaluation result: a (good retention) (test examples 8 to 34)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing property) (test examples 8-2 to 8-34)
(test examples 8-35 to 8-39)
The same measurements and evaluations as in test example 8-1 were carried out for "preparation of polymer (F6)", "preparation of positive resist composition", and "formation of resist pattern", except that the prebaking step was carried out in place of the prebaking step of heating at 110 ℃ for 10 minutes in test example 8-1, and the prebaking steps were carried out in the same manner as in test example 8-1, respectively, of heating at 100 ℃ for 10 minutes (test examples 8-35), heating at 110 ℃ for 7.5 minutes (test examples 8-36), heating at 120 ℃ for 5 minutes (test examples 8-37), heating at 130 ℃ for 3 minutes (test examples 8-38), and heating at 140 ℃ for 1 minute (test examples 8-39). The results are shown below and in fig. 3D.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284 (test examples 8-35 to 8-39)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 48614, molecular weight distribution: 1.283 (test examples 8-35)
Weight average molecular weight: 48775, molecular weight distribution: 1.286 (test examples 8 to 36)
Weight average molecular weight: 48622, molecular weight distribution: 1.286 (test examples 8-37)
Weight average molecular weight: 47171, molecular weight distribution: 1.276 (test examples 8-38)
Weight average molecular weight: 47226, molecular weight distribution: 1.285 (test 8-39)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 102.8%, retention rate evaluation result: a (good retention) (test examples 8 to 35)
Retention ratio: 103.1%, retention rate evaluation result: a (good retention) (test examples 8 to 36)
Retention ratio: 102.8%, retention rate evaluation result: a (good retention) (test examples 8 to 37)
Retention ratio: 99.7%, retention rate evaluation result: a (good retention) (test examples 8 to 38)
Retention ratio: 99.8%, retention rate evaluation result: a (good retention) (test examples 8 to 39)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: b (Low adhesion) (test examples 8-35 to 8-39)
(test examples 8 to 40)
"preparation of Polymer (F6)," preparation of Positive resist composition, "and" formation of resist Pattern "were carried out in the same manner as in test example 8-1 except that the prebaking step of heating at 110 ℃ for 10 minutes and the prebaking step of heating at 190 ℃ for 10 minutes were carried out in place of the prebaking step of heating at 110 ℃ for 10 minutes carried out in test example 8-1, and the same measurements and evaluations were carried out. The results are shown below and in fig. 3D.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 45182, molecular weight distribution: 1.323
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 95.5%, retention rate evaluation result: b (retention rate is small)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing)
Example 9
(test example 9-1)
"preparation of Polymer (F5)," preparation of Positive resist composition, "and" formation of resist Pattern "were carried out in the same manner as in test example 1-1 except that isoamyl formate was used instead of isoamyl acetate used in test example 1-1, and that a prebaking step was carried out at 110 ℃ for 10 minutes instead of the prebaking step at 120 ℃ for 10 minutes. The results are shown below and in fig. 2E.
< measurement evaluation results >
The results of the evaluation of the measured weight average molecular weight and molecular weight distribution, weight average molecular weight retention rate, and adhesion are shown below and in fig. 2E.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 51347, molecular weight distribution: 1.400
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 99.7%, retention rate evaluation result: a (good and high retention)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing)
(test examples 9-2 to 9-29)
Instead of the prebaking step of heating at 110 ℃ for 10 minutes as in test example 9-1, heating at 120 ℃ for 7.5 minutes (test example 9-2), heating at 120 ℃ for 10 minutes (test example 9-3), heating at 130 ℃ for 5 minutes (test example 9-4), heating at 130 ℃ for 7.5 minutes (test example 9-5), heating at 130 ℃ for 10 minutes (test example 9-6), heating at 140 ℃ for 3 minutes (test example 9-7), heating at 140 ℃ for 5 minutes (test example 9-8), heating at 140 ℃ for 7.5 minutes (test example 9-9), heating at 140 ℃ for 10 minutes (test example 9-10), heating at 150 ℃ for 1 minute (test example 9-11), heating at 150 ℃ for 3 minutes (test example 9-12), heating at 150 ℃ for 5 minutes (test example 9-13), heating at 150 ℃ for 7.5 minutes (test example 9-14) were carried out, A pre-baking step of heating at 150 ℃ for 10 minutes (test examples 9 to 15), heating at 160 ℃ for 1 minute (test examples 9 to 16), heating at 160 ℃ for 3 minutes (test examples 9 to 17), heating at 160 ℃ for 5 minutes (test examples 9 to 18), heating at 160 ℃ for 7.5 minutes (test examples 9 to 19), heating at 160 ℃ for 10 minutes (test examples 9 to 20), heating at 170 ℃ for 1 minute (test examples 9 to 21), heating at 170 ℃ for 3 minutes (test examples 9 to 22), heating at 170 ℃ for 5 minutes (test examples 9 to 23), heating at 170 ℃ for 7.5 minutes (test examples 9 to 24), heating at 180 ℃ for 1 minute (test examples 9 to 25), heating at 180 ℃ for 3 minutes (test examples 9 to 26), heating at 180 ℃ for 5 minutes (test examples 9 to 27), heating at 190 ℃ for 1 minute (test examples 9 to 28), and heating at 190 ℃ for 3 minutes (test examples 9 to 29), except for this, the same measurements and evaluations as in test example 9-1 were carried out for "preparation of polymer (F5)", "preparation of positive resist composition", and "formation of resist pattern". The results are shown below and in fig. 2E.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403 (test examples 9-2 to 9-29)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 51002, molecular weight distribution: 1.402 (test 9-2)
Weight average molecular weight: 51347, molecular weight distribution: 1.400 (test 9-3)
Weight average molecular weight: 50471, molecular weight distribution: 1.404 (test 9-4)
Weight average molecular weight: 50276, molecular weight distribution: 1.404 (test 9-5)
Weight average molecular weight: 50643, molecular weight distribution: 1.406 (test examples 9-6)
Weight average molecular weight: 51033, molecular weight distribution: 1.403 (test examples 9-7)
Weight average molecular weight: 49684 molecular weight distribution: 1.400 (test examples 9-8)
Weight average molecular weight: 50417, molecular weight distribution: 1.404 (test 9-9)
Weight average molecular weight: 50230, molecular weight distribution: 1.407 (test examples 9 to 10)
Weight average molecular weight: 51115, molecular weight distribution: 1.403 (test examples 9-11)
Weight average molecular weight: 51033, molecular weight distribution: 1.403 (test examples 9-12)
Weight average molecular weight: 50471, molecular weight distribution: 1.401 (test examples 9 to 13)
Weight average molecular weight: 50580, molecular weight distribution: 1.412 (test examples 9-14)
Weight average molecular weight: 50449, molecular weight distribution: 1.436 (test examples 9 to 15)
Weight average molecular weight: 51115, molecular weight distribution: 1.403 (test examples 9-16)
Weight average molecular weight: 51033, molecular weight distribution: 1.403 (test examples 9-17)
Weight average molecular weight: 50239, molecular weight distribution: 1.413 (test examples 9-18)
Weight average molecular weight: 50141, molecular weight distribution: 1.414 (test examples 9-19)
Weight average molecular weight: 50048, molecular weight distribution: 1.417 (test examples 9-20)
Weight average molecular weight: 51115, molecular weight distribution: 1.403 (test examples 9 to 21)
Weight average molecular weight: 51033, molecular weight distribution: 1.403 (test examples 9-22)
Weight average molecular weight: 49334, molecular weight distribution: 1.418 (test examples 9-23)
Weight average molecular weight: 50057, molecular weight distribution: 1.415 (test examples 9-24)
Weight average molecular weight: 51115, molecular weight distribution: 1.403 (test examples 9-25)
Weight average molecular weight: 51033, molecular weight distribution: 1.403 (test examples 9-26)
Weight average molecular weight: 49809, molecular weight distribution: 1.417 (test examples 9-27)
Weight average molecular weight: 51115, molecular weight distribution: 1.403 (test examples 9-28)
Weight average molecular weight: 51033, molecular weight distribution: 1.403 (test examples 9 to 29)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 99.0%, retention rate evaluation result: a (good retention) (test example 9-2)
Retention ratio: 99.7%, retention rate evaluation result: a (good retention) (test examples 9-3)
Retention ratio: 98.0%, retention rate evaluation result: a (good retention) (test examples 9-4)
Retention ratio: 97.6%, retention rate evaluation result: a (good retention) (test examples 9-5)
Retention ratio: 98.3%, retention rate evaluation result: a (good retention) (test examples 9-6)
Retention ratio: 99.1%, retention rate evaluation result: a (good retention) (test examples 9-7)
Retention ratio: 96.4%, retention rate evaluation result: a (good retention) (test examples 9 to 8)
Retention ratio: 97.9%, retention rate evaluation result: a (good retention) (test examples 9 to 9)
Retention ratio: 97.5%, retention rate evaluation result: a (good retention) (test examples 9 to 10)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 9 to 11)
Retention ratio: 99.1%, retention rate evaluation result: a (good retention) (test examples 9 to 12)
Retention ratio: 98.0%, retention rate evaluation result: a (good retention) (test examples 9 to 13)
Retention ratio: 98.2%, retention rate evaluation result: a (good retention) (test examples 9 to 14)
Retention ratio: 97.9%, retention rate evaluation result: a (good retention) (test examples 9 to 15)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 9 to 16)
Retention ratio: 99.1%, retention rate evaluation result: a (good retention) (test examples 9 to 17)
Retention ratio: 97.5%, retention rate evaluation result: a (good retention) (test examples 9 to 18)
Retention ratio: 97.3%, retention rate evaluation result: a (good retention) (test examples 9 to 19)
Retention ratio: 97.1%, retention rate evaluation result: a (good retention) (test examples 9-20)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 9 to 21)
Retention ratio: 99.1%, retention rate evaluation result: a (good retention) (test examples 9 to 22)
Retention ratio: 95.8%, retention rate evaluation result: a (good retention) (test examples 9 to 23)
Retention ratio: 97.2%, retention rate evaluation result: a (good retention) (test examples 9 to 24)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 9 to 25)
Retention ratio: 99.1%, retention rate evaluation result: a (good retention) (test examples 9 to 26)
Retention ratio: 96.7%, retention rate evaluation result: a (good retention) (test examples 9 to 27)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 9 to 28)
Retention ratio: 99.1%, retention rate evaluation result: a (good retention) (test examples 9 to 29)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing property) (test examples 9-2 to 9-29)
(test examples 9-30 to 9-34)
The same measurements and evaluations as in test example 9-1 were carried out for "preparation of polymer (F5)", "preparation of positive resist composition", and "formation of resist pattern" except that, instead of the prebaking step of heating at 110 ℃ for 10 minutes as carried out in test example 9-1, the prebaking steps of heating at 100 ℃ for 10 minutes (test examples 9-30), heating at 110 ℃ for 7.5 minutes (test examples 9-31), heating at 120 ℃ for 5 minutes (test examples 9-32), heating at 130 ℃ for 3 minutes (test examples 9-33), and heating at 140 ℃ for 1 minute (test examples 9-34) were carried out, respectively. The results are shown below and in fig. 2E.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403 (test examples 9-30 to 9-34)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 51347, molecular weight distribution: 1.400 (test examples 9-30)
Weight average molecular weight: 51002, molecular weight distribution: 1.402 (test examples 9-31)
Weight average molecular weight: 50734, molecular weight distribution: 1.409 (test examples 9-32)
Weight average molecular weight: 51033, molecular weight distribution: 1.403 (test examples 9 to 33)
Weight average molecular weight: 51115, molecular weight distribution: 1.403 (test examples 9-34)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 99.7%, retention rate evaluation result: a (good retention) (test examples 9 to 30)
Retention ratio: 99.0%, retention rate evaluation result: a (good retention) (test examples 9 to 31)
Retention ratio: 98.5%, retention rate evaluation result: a (good retention) (test examples 9 to 32)
Retention ratio: 99.1%, retention rate evaluation result: a (good retention) (test examples 9 to 33)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 9 to 34)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: b (Low adhesion) (test examples 9-30 to 9-34)
(test examples 9-35 to 9-37)
The same measurements and evaluations were carried out as in test example 9-1 except that, instead of the prebaking step of heating at 110 ℃ for 10 minutes as in test example 9-1, the prebaking steps of heating at 170 ℃ for 10 minutes (test examples 9-35), heating at 180 ℃ for 7.5 minutes (test examples 9-36), and heating at 190 ℃ for 5 minutes (test examples 9-37) were carried out, respectively. The results are shown below and in fig. 2E.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 48768, molecular weight distribution: 1.437 (test examples 9-35)
Weight average molecular weight: 47511, molecular weight distribution: 1.448 (test examples 9-36)
Weight average molecular weight: 47979, molecular weight distribution: 1.437 (test 9-37)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 94.7%, retention rate evaluation result: b (maintenance ratio is small) (test examples 9 to 35)
Retention ratio: 92.2%, retention rate evaluation result: b (retention ratio is small) (test examples 9 to 36)
Retention ratio: 93.1%, retention rate evaluation result: b (maintenance ratio is small) (test examples 9 to 37)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing property) (test examples 9-35 to 9-37)
Example 10
(test example 10-1)
"preparation of Polymer (F6)," preparation of Positive resist composition, "and" formation of resist Pattern "were carried out in the same manner as in test example 2-1 except that isoamyl formate was used instead of isoamyl acetate used in test example 2-1, and that a prebaking step was carried out at 110 ℃ for 10 minutes instead of the prebaking step at 120 ℃ for 10 minutes. The results are shown below and in fig. 3E.
< measurement evaluation results >
The results of the evaluation of the measured weight average molecular weight and molecular weight distribution, weight average molecular weight retention rate, and adhesion are shown below and in fig. 3E.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 48341, molecular weight distribution: 1.283
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 102.2%, retention rate evaluation result: a (good and high retention)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing)
(test examples 10-2 to 10-34)
Instead of the prebaking step of heating at 110 ℃ for 10 minutes as in test example 10-1, heating at 120 ℃ for 7.5 minutes (test example 10-2), heating at 120 ℃ for 10 minutes (test example 10-3), heating at 130 ℃ for 5 minutes (test example 10-4), heating at 130 ℃ for 7.5 minutes (test example 10-5), heating at 130 ℃ for 10 minutes (test example 10-6), heating at 140 ℃ for 3 minutes (test example 10-7), heating at 140 ℃ for 5 minutes (test example 10-8), heating at 140 ℃ for 7.5 minutes (test example 10-9), heating at 140 ℃ for 10 minutes (test example 10-10), heating at 150 ℃ for 1 minute (test example 10-11), heating at 150 ℃ for 3 minutes (test example 10-12), heating at 150 ℃ for 5 minutes (test example 10-13), heating at 150 ℃ for 7.5 minutes (test example 10-14) were carried out, Heating at 150 ℃ for 10 minutes (examples 10 to 15), heating at 160 ℃ for 1 minute (examples 10 to 16), heating at 160 ℃ for 3 minutes (examples 10 to 17), heating at 160 ℃ for 5 minutes (examples 10 to 18), heating at 160 ℃ for 7.5 minutes (examples 10 to 19), heating at 160 ℃ for 10 minutes (examples 10 to 20), heating at 170 ℃ for 1 minute (examples 10 to 21), heating at 170 ℃ for 3 minutes (examples 10 to 22), heating at 170 ℃ for 5 minutes (examples 10 to 23), heating at 170 ℃ for 7.5 minutes (examples 10 to 24), heating at 170 ℃ for 10 minutes (examples 10 to 25), heating at 180 ℃ for 1 minute (examples 10 to 26), heating at 180 ℃ for 3 minutes (examples 10 to 27), heating at 180 ℃ for 5 minutes (examples 10 to 28), and heating at 180 ℃ for 7.5 minutes (examples 10 to 29), "preparation of Polymer (F6)," preparation of Positive resist composition "and" formation of resist Pattern "were carried out in the same manner as in test example 10-1 except that the prebaking step was carried out by heating at 180 ℃ for 10 minutes (test examples 10-30), at 190 ℃ for 1 minute (test examples 10-31), at 190 ℃ for 3 minutes (test examples 10-32), at 190 ℃ for 5 minutes (test examples 10-33) and at 190 ℃ for 7.5 minutes (test examples 10-34). The results are shown below and in fig. 3E.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284 (test examples 10-2 to 10-34)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 48291 molecular weight distribution: 1.288 (test example 10-2)
Weight average molecular weight: 48341, molecular weight distribution: 1.283 (test example 10-3)
Weight average molecular weight: 46860, molecular weight distribution: 1.285 (test example 10-4)
Weight average molecular weight: 47499, molecular weight distribution: 1.276 (test example 10-5)
Weight average molecular weight: 48360, molecular weight distribution: 1.284 (test example 10-6)
Weight average molecular weight: 46862, molecular weight distribution: 1.283 (test example 10-7)
Weight average molecular weight: 46860, molecular weight distribution: 1.285 (test examples 10-8)
Weight average molecular weight: 47738, molecular weight distribution: 1.283 (test example 10-9)
Weight average molecular weight: 47391, molecular weight distribution: 1.285 (test examples 10-10)
Weight average molecular weight: 46937, molecular weight distribution: 1.288 (test examples 10 to 11)
Weight average molecular weight: 46862, molecular weight distribution: 1.285 (test examples 10-12)
Weight average molecular weight: 47557, molecular weight distribution: 1.288 (test examples 10 to 13)
Weight average molecular weight: 48006, molecular weight distribution: 1.285 (test examples 10-14)
Weight average molecular weight: 47473, molecular weight distribution: 1.289 (test examples 10-15)
Weight average molecular weight: 46937, molecular weight distribution: 1.282 (test examples 10 to 16)
Weight average molecular weight: 46862, molecular weight distribution: 1.288 (test examples 10 to 17)
Weight average molecular weight: 47324, molecular weight distribution: 1.292 (test examples 10 to 18)
Weight average molecular weight: 47596, molecular weight distribution: 1.288 (test examples 10 to 19)
Weight average molecular weight: 47044, molecular weight distribution: 1.299 (test examples 10-20)
Weight average molecular weight: 46937, molecular weight distribution: 1.284 (test examples 10 to 21)
Weight average molecular weight: 46862, molecular weight distribution: 1.293 (test examples 10-22)
Weight average molecular weight: 46492, molecular weight distribution: 1.302 (test examples 10-23)
Weight average molecular weight: 47384, molecular weight distribution: 1.293 (test examples 10-24)
Weight average molecular weight: 46531, molecular weight distribution: 1.310 (test examples 10-25)
Weight average molecular weight: 46937, molecular weight distribution: 1.291 (test examples 10-26)
Weight average molecular weight: 46862, molecular weight distribution: 1.301 (test examples 10 to 27)
Weight average molecular weight: 47314, molecular weight distribution: 1.318 (test examples 10 to 28)
Weight average molecular weight: 46909, molecular weight distribution: 1.301 (test examples 10 to 29)
Weight average molecular weight: 45554, molecular weight distribution: 1.314 (test examples 10 to 30)
Weight average molecular weight: 46937, molecular weight distribution: 1.299 (test examples 10-31)
Weight average molecular weight: 46862, molecular weight distribution: 1.306 (test examples 10 to 32)
Weight average molecular weight: 47241, molecular weight distribution: 1.318 (test examples 10 to 33)
Weight average molecular weight: 46943, molecular weight distribution: 1.319 (test examples 10-34)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 102.1%, retention rate evaluation result: a (good retention ratio) (test example 10-2)
Retention ratio: 102.2%, retention rate evaluation result: a (good retention) (test example 10-3)
Retention ratio: 99.0%, retention rate evaluation result: a (good retention) (test examples 10-4)
Retention ratio: 100.4%, retention rate evaluation result: a (good retention) (test examples 10 to 5)
Retention ratio: 102.2%, retention rate evaluation result: a (good retention) (test examples 10 to 6)
Retention ratio: 99.1%, retention rate evaluation result: a (good retention) (test examples 10 to 7)
Retention ratio: 99.0%, retention rate evaluation result: a (good retention) (test examples 10 to 8)
Retention ratio: 100.9%, retention rate evaluation result: a (good retention) (test examples 10 to 9)
Retention ratio: 100.2%, retention rate evaluation result: a (good retention) (test examples 10 to 10)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 10 to 11)
Retention ratio: 99.1%, retention rate evaluation result: a (good retention) (test examples 10 to 12)
Retention ratio: 100.5%, retention rate evaluation result: a (good retention) (test examples 10 to 13)
Retention ratio: 101.5%, retention rate evaluation result: a (good retention) (test examples 10 to 14)
Retention ratio: 100.3%, retention rate evaluation result: a (good retention) (test examples 10 to 15)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 10 to 16)
Retention ratio: 99.1%, retention rate evaluation result: a (good retention) (test examples 10 to 17)
Retention ratio: 100.0%, retention rate evaluation result: a (good retention) (test examples 10 to 18)
Retention ratio: 100.6%, retention rate evaluation result: a (good retention) (test examples 10 to 19)
Retention ratio: 99.4%, retention rate evaluation result: a (good retention ratio) (test examples 10 to 20)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 10 to 21)
Retention ratio: 99.1%, retention rate evaluation result: a (good retention) (test examples 10 to 22)
Retention ratio: 98.3%, retention rate evaluation result: a (good retention) (test examples 10 to 23)
Retention ratio: 100.2%, retention rate evaluation result: a (good retention) (test examples 10 to 24)
Retention ratio: 98.4%, retention rate evaluation result: a (good retention) (test examples 10 to 25)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 10 to 26)
Retention ratio: 99.1%, retention rate evaluation result: a (good retention) (test examples 10 to 27)
Retention ratio: 100.0%, retention rate evaluation result: a (good retention) (test examples 10 to 28)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 10 to 29)
Retention ratio: 96.3%, retention rate evaluation result: a (good retention) (test examples 10 to 30)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 10 to 31)
Retention ratio: 99.1%, retention rate evaluation result: a (good retention) (test examples 10 to 32)
Retention ratio: 99.9%, retention rate evaluation result: a (good retention) (test examples 10 to 33)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 10 to 34)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing property) (test examples 10-2 to 10-34)
(test examples 10-35 to 10-39)
The same measurements and evaluations as in test example 10-1 were carried out for "preparation of polymer (F6)", "preparation of positive resist composition", and "formation of resist pattern" except that, instead of the prebaking step of heating at 110 ℃ for 10 minutes in test example 10-1, the prebaking steps of heating at 100 ℃ for 10 minutes (test examples 10-35), heating at 110 ℃ for 7.5 minutes (test examples 10-36), heating at 120 ℃ for 5 minutes (test examples 10-37), heating at 130 ℃ for 3 minutes (test examples 10-38), and heating at 140 ℃ for 1 minute (test examples 10-39) were carried out, respectively. The results are shown below and in fig. 3E.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284 (test examples 10-35 to 10-39)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 48341, molecular weight distribution: 1.283 (test examples 10-35)
Weight average molecular weight: 48291 molecular weight distribution: 1.288 (test examples 10 to 36)
Weight average molecular weight: 46630, molecular weight distribution: 1.286 (test examples 10 to 37)
Weight average molecular weight: 46862, molecular weight distribution: 1.276 (test examples 10-38)
Weight average molecular weight: 46937, molecular weight distribution: 1.285 (test examples 10-39)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 102.2%, retention rate evaluation result: a (good retention) (test examples 10 to 35)
Retention ratio: 102.1%, retention rate evaluation result: a (good retention) (test examples 10 to 36)
Retention ratio: 98.6%, retention rate evaluation result: a (good retention) (test examples 10 to 37)
Retention ratio: 99.1%, retention rate evaluation result: a (good retention) (test examples 10 to 38)
Retention ratio: 99.2%, retention rate evaluation result: a (good retention) (test examples 10 to 39)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: b (Low adhesion) (test examples 10-35 to 10-39)
(test examples 10 to 40)
"preparation of Polymer (F6)," preparation of Positive resist composition, "and" formation of resist Pattern "were carried out in the same manner as in test example 10-1 except that the prebaking step of heating at 110 ℃ for 10 minutes and the prebaking step of heating at 190 ℃ for 10 minutes were carried out instead of the prebaking step of heating at 110 ℃ for 10 minutes carried out in test example 10-1, and the same measurements and evaluations were carried out. The results are shown below and in fig. 3E.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 45269, molecular weight distribution: 1.323
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 95.7%, retention rate evaluation result: b (retention rate is small)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing)
Example 11
(test example 11-1)
"preparation of Polymer (F5)," preparation of Positive resist composition, "and" formation of resist Pattern "were carried out in the same manner as in test example 1-1 except that n-hexyl acetate was used instead of isoamyl acetate used in test example 1-1 and that a prebaking step was carried out at 150 ℃ for 10 minutes instead of the prebaking step at 120 ℃ for 10 minutes. The results are shown below and in the lower graphs of FIGS. 2A-2E.
< measurement evaluation results >
The evaluation results of the measured weight average molecular weight and molecular weight distribution, weight average molecular weight retention ratio, and adhesion are shown below and in the lower graphs of fig. 2A to 2E.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 50473, molecular weight distribution: 1.416
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 98.0%, retention rate evaluation result: a (good and high retention)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing)
(test examples 11-2 to 11-9)
The same measurements and evaluations as in test example 11-1 were carried out except that the prebaking process of heating at 160 ℃ for 3 minutes (test example 11-2), heating at 160 ℃ for 5 minutes (test example 11-3), heating at 160 ℃ for 7.5 minutes (test example 11-4), heating at 160 ℃ for 10 minutes (test example 11-5), heating at 170 ℃ for 1 minute (test example 11-6), heating at 170 ℃ for 3 minutes (test example 11-7), heating at 170 ℃ for 5 minutes (test example 11-8), and heating at 180 ℃ for 1 minute (test example 11-9) were carried out instead of the prebaking process of heating at 150 ℃ for 10 minutes as in test example 11-1. The results are shown below and in the lower graphs of FIGS. 2A-E.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403 (test examples 11-2 to 11-9)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 50876, molecular weight distribution: 1.414 (test example 11-2)
Weight average molecular weight: 50787, molecular weight distribution: 1.417 (test example 11-3)
Weight average molecular weight: 50815, molecular weight distribution: 1.416 (test examples 11-4)
Weight average molecular weight: 50146, molecular weight distribution: 1.422 (test examples 11-5)
Weight average molecular weight: 50057, molecular weight distribution: 1.418 (test examples 11-6)
Weight average molecular weight: 50791, molecular weight distribution: 1.415 (test examples 11-7)
Weight average molecular weight: 49488, molecular weight distribution: 1.437 (test examples 11-8)
Weight average molecular weight: 50539, molecular weight distribution: 1.417 (test examples 11 to 9)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 98.7%, retention rate evaluation result: a (good retention) (test example 11-2)
Retention ratio: 98.6%, retention rate evaluation result: a (good retention) (test examples 11-3)
Retention ratio: 98.6%, retention rate evaluation result: a (good retention) (test examples 11 to 4)
Retention ratio: 97.3%, retention rate evaluation result: a (good retention) (test examples 11 to 5)
Retention ratio: 97.2%, retention rate evaluation result: a (good retention) (test examples 11 to 6)
Retention ratio: 98.6%, retention rate evaluation result: a (good retention) (test examples 11 to 7)
Retention ratio: 96.1%, retention rate evaluation result: a (good retention) (test examples 11 to 8)
Retention ratio: 98.1%, retention rate evaluation result: a (good retention) (test examples 11 to 9)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing property) (test examples 11-2 to 11-9)
(test examples 11-10 to 11-14)
The same measurements and evaluations as in test example 11-1 were carried out for "preparation of polymer (F5)", "preparation of positive resist composition", and "formation of resist pattern", except that the prebaking step was carried out for heating at 140 ℃ for 10 minutes (test examples 11 to 10), heating at 150 ℃ for 3 minutes (test examples 11 to 11), heating at 150 ℃ for 5 minutes (test examples 11 to 12), heating at 150 ℃ for 7.5 minutes (test examples 11 to 13), and heating at 160 ℃ for 1 minute (test examples 11 to 14), respectively, instead of the prebaking step at 150 ℃ for 10 minutes which was carried out in test example 11-1. The results are shown below and in the lower graphs of FIGS. 2A-E.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403 (test examples 11-10 to 11-14)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 50032, molecular weight distribution: 1.405 (test examples 11 to 10)
Weight average molecular weight: 51321, molecular weight distribution: 1.412 (test examples 11 to 11)
Weight average molecular weight: 51194, molecular weight distribution: 1.436 (test examples 11 to 12)
Weight average molecular weight: 51019, molecular weight distribution: 1.432 (test examples 11 to 13)
Weight average molecular weight: 50975, molecular weight distribution: 1.413 (test examples 11 to 14)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 97.1%, retention rate evaluation result: a (good retention) (test examples 11 to 10)
Retention ratio: 99.6%, retention rate evaluation result: a (good retention) (test examples 11 to 11)
Retention ratio: 99.4%, retention rate evaluation result: a (good retention) (test examples 11 to 12)
Retention ratio: 99.0%, retention rate evaluation result: a (good retention) (test examples 11 to 13)
Retention ratio: 98.9%, retention rate evaluation result: a (good retention) (test examples 11 to 14)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: b (Low adhesion) (test examples 11-10 to 11-14)
(test examples 11-15 to 11-21)
The same measurements and evaluations as in test example 11-1 were carried out for "preparation of polymer (F5)", "preparation of positive resist composition", and "formation of resist pattern" except that the prebaking step of heating at 170 ℃ for 7.5 minutes (test examples 11-15), heating at 170 ℃ for 10 minutes (test examples 11-16), heating at 180 ℃ for 3 minutes (test examples 11-17), heating at 180 ℃ for 5 minutes (test examples 11-18), heating at 180 ℃ for 7.5 minutes (test examples 11-19), heating at 180 ℃ for 10 minutes (test examples 11-20), and heating at 190 ℃ for 1 minute (test examples 11-21) were carried out instead of the prebaking step of heating at 150 ℃ for 10 minutes as in test example 11-1. The results are shown below and in the lower graphs of FIGS. 2A-E.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 51522, molecular weight distribution: 1.403 (test examples 11-15 to 11-21)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 49123, molecular weight distribution: 1.452 (test examples 11 to 15)
Weight average molecular weight: 47611, molecular weight distribution: 1.451 (test examples 11 to 16)
Weight average molecular weight: 48207, molecular weight distribution: 1.448 (test examples 11 to 17)
Weight average molecular weight: 47986, molecular weight distribution: 1.456 (test examples 11 to 18)
Weight average molecular weight: 47234, molecular weight distribution: 1.451 (test examples 11 to 19)
Weight average molecular weight: 46987, molecular weight distribution: 1.463 (test examples 11 to 20)
Weight average molecular weight: 48682, molecular weight distribution: 1.437 (test examples 11-21)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 95.3%, retention rate evaluation result: b (retention ratio is small) (test examples 11 to 15)
Retention ratio: 92.4%, retention rate evaluation result: b (retention ratio is small) (test examples 11 to 16)
Retention ratio: 93.6%, retention rate evaluation result: b (retention ratio is small) (test examples 11 to 17)
Retention ratio: 93.1%, retention rate evaluation result: b (retention ratio is small) (test examples 11 to 18)
Retention ratio: 91.7%, retention rate evaluation result: b (maintenance ratio is small) (test examples 11 to 19)
Retention ratio: 91.2%, retention rate evaluation result: b (retention ratio is small) (test examples 11 to 20)
Retention ratio: 94.5%, retention rate evaluation result: b (retention ratio is small) (test examples 11 to 21)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing property) (test examples 11-15 to 11-21)
Example 12
(test example 12-1)
"preparation of Polymer (F6)," preparation of Positive resist composition, "and" formation of resist Pattern "were carried out in the same manner as in test example 2-1 except that n-hexyl acetate was used instead of isoamyl acetate used in test example 2-1 and that a prebaking step was carried out at 150 ℃ for 10 minutes instead of the prebaking step at 120 ℃ for 10 minutes. The results are shown below and in the lower graphs of FIGS. 3A-3E.
< measurement evaluation results >
The evaluation results of the measured weight average molecular weight and molecular weight distribution, weight average molecular weight retention rate, and adhesion are shown below and in the lower graphs of fig. 3A to 3E.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 48317, molecular weight distribution: 1.289
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 102.1%, retention rate evaluation result: a (good and high retention)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing)
(test example 12-2 to test example 12-19)
Instead of the prebaking step of heating at 150 ℃ for 10 minutes as in test example 12-1, heating at 160 ℃ for 3 minutes (test example 12-2), heating at 160 ℃ for 5 minutes (test example 12-3), heating at 160 ℃ for 7.5 minutes (test example 12-4), heating at 160 ℃ for 10 minutes (test example 12-5), heating at 170 ℃ for 1 minute (test example 12-6), heating at 170 ℃ for 3 minutes (test example 12-7), heating at 170 ℃ for 5 minutes (test example 12-8), heating at 170 ℃ for 7.5 minutes (test example 12-9), heating at 170 ℃ for 10 minutes (test example 12-10), heating at 180 ℃ for 1 minute (test example 12-11), heating at 180 ℃ for 3 minutes (test example 12-12), heating at 180 ℃ for 5 minutes (test example 12-13), and heating at 180 ℃ for 7.5 minutes (test example 12-14) were carried out respectively, The same measurements and evaluations were carried out as in test example 12-1, except for the prebaking step of heating at 180 ℃ for 10 minutes (test examples 12-15), heating at 190 ℃ for 1 minute (test examples 12-16), heating at 190 ℃ for 3 minutes (test examples 12-17), heating at 190 ℃ for 5 minutes (test examples 12-18), and heating at 190 ℃ for 7.5 minutes (test examples 12-19). The results are shown below and in the lower graphs of FIGS. 3A-3E.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284 (test example 12-2 to test example 12-19)
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 48294, molecular weight distribution: 1.288 (test example 12-2)
Weight average molecular weight: 47739, molecular weight distribution: 1.292 (test examples 12 to 3)
Weight average molecular weight: 47543, molecular weight distribution: 1.300 (test examples 12-4)
Weight average molecular weight: 47127, molecular weight distribution: 1.299 (test examples 12-5)
Weight average molecular weight: 47174, molecular weight distribution: 1.284 (test examples 12 to 6)
Weight average molecular weight: 48079, molecular weight distribution: 1.293 (test examples 12 to 7)
Weight average molecular weight: 47218, molecular weight distribution: 1.302 (test examples 12-8)
Weight average molecular weight: 46972, molecular weight distribution: 1.313 (test examples 12-9)
Weight average molecular weight: 46546, molecular weight distribution: 1.310 (test examples 12 to 10)
Weight average molecular weight: 48008, molecular weight distribution: 1.291 (test examples 12 to 11)
Weight average molecular weight: 47597, molecular weight distribution: 1.301 (test examples 12 to 12)
Weight average molecular weight: 46227, molecular weight distribution: 1.318 (test examples 12 to 13)
Weight average molecular weight: 46231, molecular weight distribution: 1.317 (test examples 12 to 14)
Weight average molecular weight: 46266, molecular weight distribution: 1.314 (test examples 12 to 15)
Weight average molecular weight: 47934, molecular weight distribution: 1.299 (test examples 12 to 16)
Weight average molecular weight: 47165, molecular weight distribution: 1.306 (test examples 12 to 17)
Weight average molecular weight: 45937, molecular weight distribution: 1.318 (test examples 12 to 18)
Weight average molecular weight: 45542, molecular weight distribution: 1.323 (test examples 12 to 19)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 102.1%, retention rate evaluation result: a (good retention ratio) (test example 12-2)
Retention ratio: 100.9%, retention rate evaluation result: a (good retention) (test examples 12 to 3)
Retention ratio: 100.5%, retention rate evaluation result: a (good retention) (test examples 12 to 4)
Retention ratio: 99.6%, retention rate evaluation result: a (good retention) (test examples 12 to 5)
Retention ratio: 99.7%, retention rate evaluation result: a (good retention) (test examples 12 to 6)
Retention ratio: 101.6%, retention rate evaluation result: a (good retention) (test examples 12 to 7)
Retention ratio: 99.8%, retention rate evaluation result: a (good retention) (test examples 12 to 8)
Retention ratio: 99.3%, retention rate evaluation result: a (good retention) (test examples 12 to 9)
Retention ratio: 98.4%, retention rate evaluation result: a (good retention ratio) (test examples 12 to 10)
Retention ratio: 101.5%, retention rate evaluation result: a (good retention) (test examples 12 to 11)
Retention ratio: 100.6%, retention rate evaluation result: a (good retention) (test examples 12 to 12)
Retention ratio: 97.7%, retention rate evaluation result: a (good retention) (test examples 12 to 13)
Retention ratio: 97.7%, retention rate evaluation result: a (good retention) (test examples 12 to 14)
Retention ratio: 97.8%, retention rate evaluation result: a (good retention) (test examples 12 to 15)
Retention ratio: 101.3%, retention rate evaluation result: a (good retention) (test examples 12 to 16)
Retention ratio: 99.7%, retention rate evaluation result: a (good retention) (test examples 12 to 17)
Retention ratio: 97.1%, retention rate evaluation result: a (good retention) (test examples 12 to 18)
Retention ratio: 96.3%, retention rate evaluation result: a (good retention) (test examples 12 to 19)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good adhesion) (test examples 12-2 to 12-19)
(test examples 12-20 to 12-24)
The same measurements and evaluations as in test example 12-1 were carried out for "preparation of polymer (F6)", "preparation of positive resist composition", and "formation of resist pattern", except that the prebaking step was carried out in place of the prebaking step of heating at 150 ℃ for 10 minutes in test example 12-1, and the prebaking steps were carried out in the same manner as in test example 12-1, respectively, of heating at 140 ℃ for 10 minutes (test examples 12-20), heating at 150 ℃ for 3 minutes (test examples 12-21), heating at 150 ℃ for 5 minutes (test examples 12-22), heating at 150 ℃ for 7.5 minutes (test examples 12-23), and heating at 160 ℃ for 1 minute (test examples 12-24). The results are shown below and in the lower graphs of FIGS. 3A-3E.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 47664, molecular weight distribution: 1.285 (test examples 12-20)
Weight average molecular weight: 48710, molecular weight distribution: 1.285 (test examples 12 to 21)
Weight average molecular weight: 48174, molecular weight distribution: 1.288 (test examples 12 to 22)
Weight average molecular weight: 48312, molecular weight distribution: 1.291 (test examples 12 to 23)
Weight average molecular weight: 48018, molecular weight distribution: 1.282 (test examples 12 to 24)
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 100.7%, retention rate evaluation result: a (good retention ratio) (test examples 12 to 20)
Retention ratio: 103.0%, retention rate evaluation result: a (good retention) (test examples 12 to 21)
Retention ratio: 101.8%, retention rate evaluation result: a (good retention) (test examples 12 to 22)
Retention ratio: 102.1%, retention rate evaluation result: a (good retention) (test examples 12 to 23)
Retention ratio: 101.5%, retention rate evaluation result: a (good retention) (test examples 12 to 24)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: b (Low adhesion) (test examples 12-20 to 12-24)
(test examples 12 to 25)
"preparation of Polymer (F6)," preparation of Positive resist composition, "and" formation of resist Pattern "were carried out in the same manner as in test example 12-1 except that the prebaking step of heating at 150 ℃ for 10 minutes and the prebaking step of heating at 190 ℃ for 10 minutes were carried out in place of the prebaking step of heating at 150 ℃ for 10 minutes carried out in test example 12-1, and the same measurements and evaluations were carried out. The results are shown below and in the lower graphs of FIGS. 3A-3E.
(i) Weight average molecular weight and molecular weight distribution of the produced polymer
Weight average molecular weight: 47311, molecular weight distribution: 1.284
(ii) Weight average molecular weight and molecular weight distribution of polymer in resist film formed via a prebaking process
Weight average molecular weight: 45219, molecular weight distribution: 1.323
(iii) Retention of polymer weight average molecular weight in resist film formed via a prebaking process
Retention ratio: 95.6%, retention rate evaluation result: b (retention rate is small)
(iv) Adhesion between resist film formed by prebaking and workpiece
Evaluation results of adhesion: a (good sealing)
As is apparent from fig. 2A to E, a positive resist composition (upper diagrams in fig. 2A to E: examples 1, 3, 5, 7, and 9) containing a predetermined polymer (F5) having a predetermined monomer unit and at least one solvent selected from isoamyl acetate, n-butyl formate, isobutyl formate, n-amyl formate, and isoamyl formate as a solvent can improve the adhesion between a resist film formed through a pre-baking step and a work and reduce the change in the molecular weight of the polymer in the resist film before and after the pre-baking step in a wider range of the pre-baking temperature T and the pre-baking time T (lower diagrams in fig. 2A to E: comparative example 1) than a positive resist composition (upper diagrams in fig. 2A to E: examples 1) containing a predetermined polymer (F5) having a predetermined monomer unit and n-hexyl acetate.
As is apparent from fig. 3A to E, the positive resist composition (upper diagrams in fig. 3A to E: examples 2, 4, 6, 8, and 10) containing a predetermined polymer (F6) having a predetermined monomer unit and at least one solvent selected from isoamyl acetate, n-butyl formate, isobutyl formate, n-amyl formate, and isoamyl formate as a solvent can improve the adhesion between a resist film formed through a pre-baking step and a work and reduce the change in the molecular weight of the polymer in the resist film before and after the pre-baking step at a wider range of the pre-baking temperature T and the pre-baking time T (lower diagrams in fig. 3A to E: comparative example 2) than the positive resist composition (upper diagrams in fig. 3A to E: examples 2) containing a predetermined polymer (F6) having a predetermined monomer unit and n-hexyl acetate.
Industrial applicability
According to the positive resist composition of the present invention, it is possible to improve the adhesion between the resist film formed through the prebaking process and the workpiece in a wider range of heating temperature and heating time in the prebaking process (heating temperature in a range on the lower temperature side), and to reduce the change in the molecular weight of the polymer in the resist film before and after the prebaking process.
Further, according to the resist film forming method of the present invention, it is possible to improve the adhesion between the resist film formed through the pre-baking step and the object to be processed, and to reduce the change in the molecular weight of the polymer in the resist film before and after the pre-baking step.
Further, according to the method for producing a laminate of the present invention, adhesion between the resist film formed through the prebaking step and the light shielding layer can be improved, and a decrease in the molecular weight of the polymer in the resist film can be suppressed.

Claims (11)

1. A positive resist composition comprising a polymer and a solvent,
the polymer has a monomer unit A represented by the following general formula (I) and a monomer unit B represented by the following general formula (II),
Figure FDA0002405838380000011
in the formula (I), R1Is a chlorine atom, a fluorine atom or a fluorine atom-substituted alkyl group (substituted with a fluorine atom), R2Is unsubstituted alkyl or alkyl substituted by fluorine atoms, R3And R4Hydrogen atom, fluorine atom, unsubstituted alkyl group or fluorine atom-substituted alkyl group, which may be the same or different from each other,
Figure FDA0002405838380000012
in the formula (II), R5、R6、R8And R9Is a hydrogen atom, a fluorine atom, an unsubstituted alkyl group or a fluorine atomSubstituted alkyl groups, which may be the same or different from each other, R7Is a hydrogen atom, an unsubstituted alkyl group or a fluorine atom-substituted alkyl group, p and q are integers of 0 to 5 inclusive, p + q is 5,
at least one of the monomer unit A and the monomer unit B has one or more fluorine atoms,
the solvent is at least 1 selected from isoamyl acetate, n-butyl formate, isobutyl formate, n-amyl formate and isoamyl formate.
2. The positive resist composition according to claim 1, wherein R is1Is a chlorine atom.
3. The positive resist composition according to claim 2, wherein R is2Is an alkyl group substituted with a fluorine atom,
the R is3And R4The hydrogen atoms or the unsubstituted alkyl groups may be the same or different from each other.
4. The positive resist composition according to any one of claims 1 to 3, wherein p is an integer of 1 or more and 5 or less, R5And R7～R9Is a hydrogen atom or an unsubstituted alkyl group,
the monomer unit A has one or more fluorine atoms.
5. The positive resist composition according to claim 4, wherein the number of fluorine atoms in the monomer unit B is 0 or 1.
6. The positive resist composition according to any one of claims 1 to 5, wherein R is2Is a pentafluoroalkyl group.
7. The positive resist composition according to any one of claims 1 to 6, wherein R is2Is 2,2,3,3, 3-pentafluoropropyl.
8. The positive resist composition according to any one of claims 1 to 7, wherein the monomer unit B is a structural unit derived from α -methylstyrene or a structural unit derived from 4-fluoro- α -methylstyrene.
9. A resist film forming method for forming a resist film using the positive resist composition according to any one of claims 1 to 8, comprising:
a coating step of coating the positive resist composition on a workpiece; and
a prebaking step of heating the applied positive resist composition,
the heating in the pre-baking step is performed at a temperature T and a time T satisfying the following formula (1), the temperature being in units of DEG C, the time being in units of minutes,
(-1/4)×T+32.5≤t≤(-1/4)×T+55…(1)。
10. the resist film formation method according to claim 9, wherein the time is 1 minute or more and 30 minutes or less.
11. A method for producing a laminate, comprising a substrate, a light-shielding layer formed on the substrate, and a resist film formed on the light-shielding layer, wherein the resist film is formed by the resist film formation method according to claim 9 or 10.
CN201880058649.5A 2017-09-29 2018-08-23 Positive resist composition, method for forming resist film, and method for producing laminate Active CN111065967B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2017-191620 2017-09-29
JP2017191620 2017-09-29
PCT/JP2018/031212 WO2019065017A1 (en) 2017-09-29 2018-08-23 Positive resist composition, resist film formation method, and method for producing laminate

Publications (2)

Publication Number Publication Date
CN111065967A true CN111065967A (en) 2020-04-24
CN111065967B CN111065967B (en) 2023-06-23

Family

ID=65901706

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201880058649.5A Active CN111065967B (en) 2017-09-29 2018-08-23 Positive resist composition, method for forming resist film, and method for producing laminate

Country Status (6)

Country Link
US (1) US11402753B2 (en)
JP (1) JP7131560B2 (en)
KR (1) KR102656151B1 (en)
CN (1) CN111065967B (en)
TW (1) TWI782092B (en)
WO (1) WO2019065017A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018202603A1 (en) * 2017-05-03 2018-11-08 Merck Patent Gmbh Formulation of an organic functional material

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57118243A (en) * 1981-01-14 1982-07-23 Toshiba Corp Formation of fine resist pattern
JPS5949536A (en) * 1982-09-14 1984-03-22 Toshiba Corp Formation of micropattern
JPS61170735A (en) * 1985-01-25 1986-08-01 Toray Ind Inc Preparation of fluoroalkyl alpha-chloroacrylate polymer or copolymer
JPS6446748A (en) * 1987-08-17 1989-02-21 Fujitsu Ltd Method for applying and forming chloromethylated polystyrene resist
JPH05249684A (en) * 1991-12-26 1993-09-28 Toppan Printing Co Ltd Positive electron beam resist composition
JPH0798502A (en) * 1993-09-29 1995-04-11 Tosoh Corp Positive type thermosetting photosensitive material
WO1999062964A1 (en) * 1998-06-04 1999-12-09 Nippon Zeon Co., Ltd. PURIFIED METHYL α-CHLOROACRYLATE/α-METHYLSTYRENE COPOLYMER AND ELECTRON BEAM RESIST COMPOSITION CONTAINING THE SAME
US6451512B1 (en) * 2000-05-01 2002-09-17 Advanced Micro Devices, Inc. UV-enhanced silylation process to increase etch resistance of ultra thin resists
WO2008087840A1 (en) * 2007-01-19 2008-07-24 Jsr Corporation Radiation-sensitive resin composition for immersion exposure and method of forming photoresist pattern
US20100203450A1 (en) * 2009-02-11 2010-08-12 International Business Machines Corporation Photoresist compositions and methods of use
US20160363866A1 (en) * 2015-06-09 2016-12-15 Shin-Etsu Chemical Co., Ltd. Patterning process
US20170003590A1 (en) * 2015-06-30 2017-01-05 Shin-Etsu Chemical Co., Ltd. Resist composition and patterning process
WO2017130873A1 (en) * 2016-01-29 2017-08-03 日本ゼオン株式会社 Resist pattern forming method

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1164261A (en) * 1981-04-21 1984-03-27 Tsukasa Tada PROCESS FOR FORMING RESIST PATTERNS BY DEVELOPING A POLYMER CONTAINING TRIFLUOROETHYL-.alpha.- CHLOROCRYLATE UNITS WITH SPECIFIC KETONE COMPOUNDS
JPH083636B2 (en) 1986-11-29 1996-01-17 富士通株式会社 Electron beam positive resist
JPH02115852A (en) * 1988-10-26 1990-04-27 Fujitsu Ltd Production of semiconductor device
TWI237162B (en) * 2000-08-15 2005-08-01 Fuji Photo Film Co Ltd Electron radiation- or X ray-resist composition
US6645695B2 (en) * 2000-09-11 2003-11-11 Shipley Company, L.L.C. Photoresist composition
JP5249684B2 (en) 2008-09-04 2013-07-31 三菱重工業株式会社 Windmill wing
WO2011125690A1 (en) 2010-04-01 2011-10-13 住友化学株式会社 Composition, containing a fluorine organic compound solvent, for use in an organic thin-film transistor insulation layer
JP5618625B2 (en) 2010-05-25 2014-11-05 富士フイルム株式会社 Pattern forming method and actinic ray-sensitive or radiation-sensitive resin composition
WO2014017144A1 (en) 2012-07-27 2014-01-30 Jsr株式会社 Method for forming negative resist pattern and photoresist composition
WO2016104565A1 (en) 2014-12-26 2016-06-30 富士フイルム株式会社 Organic treatment solution and pattern-forming method
KR102641396B1 (en) * 2015-02-20 2024-02-26 니폰 제온 가부시키가이샤 Polymer and positive resist compositions
CN108473627B (en) * 2016-01-29 2020-09-15 日本瑞翁株式会社 Polymer, positive resist composition and method for forming resist pattern
JP5938536B1 (en) * 2016-03-25 2016-06-22 日本ゼオン株式会社 Method for producing copolymer
CN109804311B (en) * 2016-10-12 2023-06-06 默克专利有限公司 Chemically amplified positive photoresist composition and pattern forming method using the same
WO2018123667A1 (en) * 2016-12-27 2018-07-05 日本ゼオン株式会社 Polymer, positive resist composition, and resist pattern formation method
CN111480116B (en) * 2018-02-05 2023-05-30 日本瑞翁株式会社 Method for forming resist pattern
US11988964B2 (en) * 2018-04-27 2024-05-21 Zeon Corporation Positive resist composition for EUV lithography and method of forming resist pattern
WO2020066806A1 (en) * 2018-09-25 2020-04-02 日本ゼオン株式会社 Copolymer and positive resist composition
JP7098502B2 (en) 2018-10-16 2022-07-11 株式会社東芝 Reporting equipment, methods, and programs

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57118243A (en) * 1981-01-14 1982-07-23 Toshiba Corp Formation of fine resist pattern
JPS5949536A (en) * 1982-09-14 1984-03-22 Toshiba Corp Formation of micropattern
JPS61170735A (en) * 1985-01-25 1986-08-01 Toray Ind Inc Preparation of fluoroalkyl alpha-chloroacrylate polymer or copolymer
JPS6446748A (en) * 1987-08-17 1989-02-21 Fujitsu Ltd Method for applying and forming chloromethylated polystyrene resist
JPH05249684A (en) * 1991-12-26 1993-09-28 Toppan Printing Co Ltd Positive electron beam resist composition
JPH0798502A (en) * 1993-09-29 1995-04-11 Tosoh Corp Positive type thermosetting photosensitive material
WO1999062964A1 (en) * 1998-06-04 1999-12-09 Nippon Zeon Co., Ltd. PURIFIED METHYL α-CHLOROACRYLATE/α-METHYLSTYRENE COPOLYMER AND ELECTRON BEAM RESIST COMPOSITION CONTAINING THE SAME
US6451512B1 (en) * 2000-05-01 2002-09-17 Advanced Micro Devices, Inc. UV-enhanced silylation process to increase etch resistance of ultra thin resists
WO2008087840A1 (en) * 2007-01-19 2008-07-24 Jsr Corporation Radiation-sensitive resin composition for immersion exposure and method of forming photoresist pattern
US20100203450A1 (en) * 2009-02-11 2010-08-12 International Business Machines Corporation Photoresist compositions and methods of use
US20160363866A1 (en) * 2015-06-09 2016-12-15 Shin-Etsu Chemical Co., Ltd. Patterning process
US20170003590A1 (en) * 2015-06-30 2017-01-05 Shin-Etsu Chemical Co., Ltd. Resist composition and patterning process
WO2017130873A1 (en) * 2016-01-29 2017-08-03 日本ゼオン株式会社 Resist pattern forming method

Also Published As

Publication number Publication date
TWI782092B (en) 2022-11-01
JPWO2019065017A1 (en) 2020-09-10
US11402753B2 (en) 2022-08-02
US20200257198A1 (en) 2020-08-13
KR102656151B1 (en) 2024-04-08
CN111065967B (en) 2023-06-23
KR20200054208A (en) 2020-05-19
JP7131560B2 (en) 2022-09-06
WO2019065017A1 (en) 2019-04-04
TW201915035A (en) 2019-04-16

Similar Documents

Publication Publication Date Title
KR101931856B1 (en) Polymer for resist under layer film composition, resist under layer film composition, and patterning process
TWI752001B (en) Compound, resin, composition, method for forming resist pattern, and method for forming circuit pattern
JP6365015B2 (en) POSITIVE RESIST COMPOSITION AND METHOD FOR PRODUCING THE SAME, AND METHOD FOR PRODUCING RESIST PATTERN USING THE POSITIVE RESIST COMPOSITION
CN110050005B (en) Polymer, positive resist composition, and resist pattern formation method
JP6609193B2 (en) Polymer compound, negative resist composition, laminate, pattern forming method, and compound
TWI723995B (en) Pre-cleaning liquid, pre-cleaning treatment method and pattern forming method
KR20140104420A (en) Resist-underlayer-film-forming composition used in multilayer resist process, resist underlayer film, method for forming same, and pattern-formation method
KR20140018268A (en) Resist pattern forming method, resist pattern, crosslinkable negative chemical amplification resist composition for organic solvent development, resist film and resist-coated mask blanks
CN103694404A (en) Phenolic polymer and photoresist comprising same
CN111164511A (en) Composition for lithography, pattern formation method, and compound
CN105867069A (en) Negative-type photosensitive resin composition, photocuring pattern formed by using the same and image display device
US10520814B2 (en) Resist underlayer film-forming composition, resist underlayer film, resist underlayer film-forming process, and production method of patterned substrate
US10551737B2 (en) Method for forming resist underlayer film
CN111065967A (en) Positive resist composition, method for forming resist film, and method for producing laminate
TWI783111B (en) Photoresist Pattern Formation Method
CN106243513A (en) The compositions processed for pattern and method
JP6958040B2 (en) Laminate
WO2019208354A1 (en) Positive resist composition for euv lithography and resist pattern forming method
KR102230712B1 (en) Organic copolymer, process of synthesizing the organic copolymer, anti-reflection filim including the organic copolymer and application thereof
EP3693793A1 (en) Resin material for forming underlayer film, resist underlayer film, method for producing resist underlayer film, and layered product
US20190203067A1 (en) Composition, insulating material, and method for preparing an insulating material
JP6958039B2 (en) Resist film forming method and laminate manufacturing method
KR20130113998A (en) Photosensitive resin composition for forming black column spacer, black column spacer, display device, and method for forming blcak column spacer
WO2019151019A1 (en) Positive-type resist composition, resist film formation method, and laminate production method
JP2019133104A (en) Positive resist composition, method for forming resist film, and method for manufacturing laminate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant